2-[(1h-pyrazol-4-ylmethyl) -sulfonyl] -oxazol-derivative, 2-[(1h-pyrazol-4-ylmethyl) -sulfanyl] -oxazol-derivatives, and chiral 2-[(1h-pyrazol-4-ymethyl)sulfinyl]oxazole derivatives, methods for the production thereof as herbicides and plant growth regulators

ABSTRACT

The invention relates to 2-[(1H-pyrazol-4-ylmethyl)-sulfonyl]-oxazole derivatives, chiral 2-[(1H-pyrazol-4-ylmethyl)-sulfinyl]-oxazole derivatives, and 2-[(1H-pyrazol-4-ylmethyl)-sulfanyl]-oxazole derivatives of general formula (I) and the salts thereof, methods for the production thereof, and the use thereof as herbicides and plant growth regulators, in particular as herbicides for selectively controlling weeds in plant crops.

The present invention relates to 2-[(1H-pyrazol-4-ylmethyl)sulfonyl]oxazole derivatives, chiral 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]oxazole derivatives, and 2-[(1H-pyrazol-4-ylmethyl)sulfanyl]oxazole derivatives, and to specific processes for their preparation. The present invention furthermore provides their use as herbicide, in particular as herbicide for the selective control of harmful plants in crops of useful plants, as plant growth regulators on their own or in combination with safeners and/or as a mixture with other herbicides.

It is already known from various publications that certain oxazole derivatives have herbicidal and pesticidal properties.

Thus, WO 2004/013112 A describes herbicidally active oxazole derivatives which have a fluoroalkene-containing thioether group at the 2-position of the oxazole ring.

U.S. Pat. No. 4,022,607 describes 2-(alkylsulfinyl)oxazole derivatives, their preparation and their use as herbicide.

DE 10 254 876 A describes 2-(fluoroalkenylthio)oxazoles and their use as herbicides.

EP 0 435 794 A describes 1-heterocyclylsulfonyl-2-phenyl-2-propenes and their use as herbicides.

Pesticidal properties of 2-trifluorobutenethiooxazole derivatives are described, for example, in WO 2001/066529 A, WO 99/52874 A and WO 95/024403 A.

1-Alkyl-5-nitroimidazolyl 2-alkylheteroaryl sulfides in which the heteroaryl is a substituted oxazole are described in DE 23 59 922 A.

2-[(1H-Pyrazol-4-ylmethyl)sulfinyl] and 2-[(1H-pyrazol-4-ylmethyl)sulfonyl] derivatives having herbicidal properties have also been described. Thus, WO 2007/071900 A, WO 02/62770 A and WO 2006/123088 describe a number of 2-[(1H-pyrazol-4-ylmethyl)sulfinyl] and 2-[(1H-pyrazol-4-ylmethyl)sulfonyl] derivatives which carry a suitable substituted (1H-pyrazol-4-ylmethyl) group as substituent at the 2-sulfonyl or 2-sulfinyl group. The publications mentioned above also describe a process for their preparation.

2-(Arylmethylsulfonyl)-substituted derivatives having herbicidal properties have also been described. Thus, JP 2003/096059 A, WO 2001/112613 A and U.S. Pat. No. 3,960,542 describe a number of 2-(arylmethylsulfonyl) derivatives having a suitable substituted phenylmethyl group as substituent at the 2-sulfonyl group. The publications mentioned above also describe a process for their preparation.

However, the active compounds already known from the publications mentioned above, when used as herbicides, have disadvantages, be it (a) that they have insufficient, if any, herbicidal activity against harmful plants, (b) that the spectrum of harmful plants which can be controlled by one active compound is not wide enough, or (c) that their selectivity in crops of useful plants is too low.

For these reasons, it is desirable to provide alternative chemical active compounds which can be employed as herbicides or plant growth regulators, if appropriate with advantages.

The present invention now provides 2-[(1H-pyrazol-4-ylmethyl)sulfonyl]oxazole derivatives, chiral 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]oxazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfanyl]oxazole derivatives which have advantages compared to the compounds described in the prior art.

Accordingly, the present invention provides compounds of the formula (I) according to the invention and agrochemically acceptable salts thereof

-   -   in which the radicals and indices have the following meaning:     -   n is 0, 1 or 2;     -   the substituents R¹ and R² are each independently of one another         selected from the group consisting of         -   hydrogen, halogen, nitro, cyano, formyl, C(O)OH, hydroxyl,             amino,         -   (C₁-C₆)-alkyl, (C₁-C₆)-alkylcarbonyl,             (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl,         -   (C₁-C₆)-alkylcarbonyloxy, (C₁-C₆)-alkoxy,             (C₁-C₆)-alkoxycarbonyl,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy,         -   (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy,         -   (C₂-C₆)-alkenyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyl,             (C₂-C₆)-alkynyloxy,         -   (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl,             (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylsulfonyloxy,             (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkyl-sulfinyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy,         -   mono-((C₁-C₆)-alkyl)amino, di-((C₁-C₆)-alkyl)amino,             N—((C₁-C₆)-alkanoyl)amino, aminocarbonyl-(C₁-C₆)-alkyl,             mono-((C₁-C₆)-alkyl)aminocarbonyl,             di-((C₁-C₆)-alkyl)aminocarbonyl,             mono-((C₁-C₆)-alkyl)aminosulfonyl,             di-((C₁-C₆)-alkyl)aminosulfonyl,         -   (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy,             (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl,         -   (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy,             (C₃-C₆)-cycloalkylthio, (C₃-C₈)-cycloalkylsulfinyl,             (C₃-C₈)-cycloalkylsulfonyl, (C₃-C₈)-cyclo-alkylsulfonyloxy,         -   cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl,             —CONN—SO₂—(C₁-C₆)-alkyl, —NHCHO, —NHCO—(C₁-C₆)-alkyl,             —NHCO₂—(C₁-C₆)-alkyl, —NHCONH—(C₁-C₆)-alkyl,             —NHSO₂—(C₁-C₆)-alkyl, —OCONH—(C₁-C₆)-alkyl,             (C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl,             di-(C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl,         -   —C(O)NHR⁹, —C(O)NR⁹R¹⁰,             -   where R⁹ and R¹⁰ are independently of one another                 hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,                 (C₁-C₆)-haloalkyl, or             -   where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group                 which may contain an oxygen or a sulfur atom or one or                 two amino or (C₁-C₆)-alkylamino groups,     -   where the abovementioned radicals R¹ and R² may be mono- or         polysubstituted independently of one another;         -   the substituents R³ to R⁵ are each independently of one             another selected from the group consisting of             -   hydrogen, halogen, hydroxyl, cyano, nitro, amino,                 C(O)OH, formyl,             -   (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl,                 (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy,                 (C₁-C₆)-haloalkyl-carbonyloxy,                 (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl,                 (C₁-C₆)-haloalkyl-carbonyl-(C₁-C₄)-alkyl,                 (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl,                 (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl,             -   (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,                 (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-haloalkoxycarbonyl,                 (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl,             -   (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,                 (C₂-C₆)-alkenylcarbonyl, (C₂-C₆)-haloalkenylcarbonyl,                 (C₂-C₆)-alkenyloxy, (C₂-C₆)-halo-alkenyloxy,                 (C₂-C₆)-alkenyloxycarbonyl,                 (C₂-C₆)-haloalkenyl-oxycarbonyl,             -   (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl,                 (C₂-C₆)-alkynylcarbonyl, (C₂-C₆)-haloalkynylcarbonyl,                 (C₂-C₆)-alkynyloxy, (C₂-C₆)-halo-alkynyloxy,                 (C₂-C₆)-alkynyloxycarbonyl,                 (C₂-C₆)-haloalkynyloxy-carbonyl,             -   (C₁-C₆)-alkylthiocarbonyl,                 (C₁-C₆)-haloalkylthiocarbonyl, alkylthiocarbonyloxy,                 (C₁-C₆)-haloalkylthiocarbonyloxy,             -   (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy,                 (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl-carbonyl,                 (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy,             -   (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl,                 (C₆-C₁₄)-aryloxycarbonyl,             -   (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl,                 (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy,                 (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl,                 (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyl,                 (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyloxy,                 (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy-carbonyl,                 (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy,             -   (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio,                 (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-haloalkylsulfonyl,                 (C₁-C₆)-haloalkylthio, (C₁-C₆)-haloalkyl-sulfinyl,                 (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl,                 (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-haloalkyl-sulfonyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl,                 haloalkylsulfinyl-(C₁-C₆)-alkyl,                 (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl,                 (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkyl-sulfonyloxy,             -   (C₄-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio,                 (C₆-C₁₄)-arylsulfinyl,             -   mono-((C₁-C₆)-alkyl)amino,                 mono-((C₁-C₆)-haloalkyl)amino, di-((C₁-C₆)-alkyl)amino,                 di-((C₁-C₆)-haloalkyl)amino,                 ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)amino,                 N—((C₁-C₆)-alkanoyl)amino,                 N—((C₁-C₆)-haloalkanoyl)amino,                 aminocarbonyl-(C₁-C₆)-alkyl,                 mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,                 di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,                 mono-((C₁-C₆)-alkyl)aminocarbonyl,                 (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl,                 (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy,                 (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy,             -   (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy,                 (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-halo-alkylcarbonyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl,                 (C₃-C₈)-cycloalkylcarbonyl-oxy,                 (C₃-C₈)-cycloalkoxycarbonyloxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy,                 (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyloxy,             -   (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy,                 (C₃-C₈)-cyclo-alkenyl-(C₁-C₆)-alkyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy,                 (C₃-C₈)-cycloalkenylcarbonyl,                 (C₃-C₈)-cycloalkenyloxy-carbonyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy-carbonyl,                 (C₃-C₈)-cycloalkenylcarbonyloxy,                 (C₃-C₈)-cycloalkenyl-oxycarbonyloxy,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy,                 (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy,             -   (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio,                 (C₃-C₈)-cycloalkenyl-thio, (C₃-C₆)-alkynylthio,             -   hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy,                 cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl,             -   3-oxetanyloxy-,             -   —C(O)NR⁹R¹⁰,                 -   where R⁹ and R¹⁰ are independently of one another                     hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl or                     (C₁-C₆)-haloalkyl, or                 -   where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene                     group which may contain an oxygen or a sulfur atom                     or one or two amino or (C₁-C₆)-alkylamino groups,         -   where the abovementioned radicals R³ to R⁵ may be mono- or             polysubstituted independently of one another, and/or         -   adjacent radicals R⁴ and R⁵ may be cyclically attached to             one another and/or form a (C₁-C₆)-alkylene group which may             contain one or more oxygen and/or sulfur atoms, where the             (C₁-C₆)-alkylene group may be mono- or polysubstituted by             halogen and the respective halogen substituents may be             identical or different.

If the radicals, in particular radicals comprising an aryl group, a cycloalkyl group, an alkyl group, an alkenyl group, an alkynyl group and a cycloalkenyl group, comprise one or more substituents, such as, for example, cycloalkyl or aryl, the substituents are preferably selected from the group consisting of (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, nitro, cyano, (C₁-C₃)-cycloalkyl, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl or halogen, where the radicals mentioned may optionally be cyclically attached to one another, with the proviso that they are ortho to one another.

A first embodiment of the present invention comprises compounds of the formula (I) in which

-   R¹ is preferably selected from the group consisting of H, halogen,     nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,     (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl,     (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl,     (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)aminocarbonyl,     di-((C₁-C₄)-alkyl)aminocarbonyl, mono-((C₁-C₄)-alkyl)aminosulfonyl,     di-((C₁-C₄)-alkyl)aminosulfonyl, (C₁-C₄)-alkylthio,     (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl,     (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,     (C₃-C₆)-cycloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy,     (C₃-C₆)-cyclo-alkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl,     (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl,     —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl,     —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, —CONR⁹R¹⁰, where R⁹ and R¹⁰ are     independently of one another selected from the group consisting of     hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl and (C₁-C₆)-haloalkyl;     and     -   where the abovementioned radical R¹ may be mono- or         polysubstituted independently of one another by radicals         selected from the group consisting of halogen and (C₁-C₆)-alkyl, -   R¹ is particularly -   preferably selected from the group consisting of H, F, Cl, Br, I,     Me, Et, NO₂, CHF₂ and CF₃; and -   R¹ is very particularly -   preferably selected from the group consisting of H, F, Cl, Br, I and     Me.

A second embodiment of the present invention comprises compounds of the formula (I) in which

-   R² is preferably selected from the group consisting of H, halogen,     nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,     (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl,     (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl,     (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)aminocarbonyl,     di-((C₁-C₄)-alkyl)aminocarbonyl, mono-((C₁-C₄)-alkyl)aminosulfonyl,     di-((C₁-C₄)-alkyl)aminosulfonyl, (C₃-C₆)-cycloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₃-C₆)-cycloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cycloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, (C₃-C₆)-cyclo-alkylsulfonyloxy,     (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-alkenyloxy,     (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl, —NHCO₂—(C₁-C₃)-alkyl,     —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl,     —CONHR⁹, —CONR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one     another hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-haloalkyl,     -   where the abovementioned radical R² may be mono- or         polysubstituted independently of one another by radicals         selected from the group consisting of halogen and (C₁-C₆)-alkyl; -   R² is particularly -   preferably selected from the group consisting of H, F, Cl, Br, I,     Me, Et, NO₂, CHF₂ and CF₃; and -   R² is very particularly -   preferably selected from the group consisting of H, F, Cl and Br.

A third embodiment of the present invention comprises compounds of the formula (I) in which

-   R³ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂-alkyl), di-(C₁-C₄)-alkylamino,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy,     hydroxy-(C₁-C₂)-alkyl, hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy,     cyano-(C₁-C₂)-alkyl; phenyl which is optionally substituted by one     or more identical or different radicals from the group consisting of     halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkyl which is optionally     substituted by one or more identical or different radicals from the     group consisting of halogen, nitro, cyano, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkoxy, phenoxy which is     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, nitro, cyano,     (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy or (C₁-C₆)-alkylthio;     (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently     of one another selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups;     -   and -   R³ is particularly -   preferably selected from the group consisting of H, F, Cl, Br, I,     CN, Me, Et, Pr, iPr, tBu, CHF₂, CF₃, OMe, OEt, OCHF₂ and OCH₂CF₃;     and -   R³ is very particularly -   preferably selected from the group consisting of F, Cl, Br, CHF₂,     CF₃, OCHF₂, OCF₃, OCH₂CF₃, Me, OMe, Pr, iPr and Et.

A fourth embodiment of the present invention comprises compounds of the formula (I) in which

-   R⁴ is preferably selected from the group consisting of hydrogen;     (C₁-C₄)-alkyl; (C₁-C₄)-haloalkyl; phenyl which is optionally     substituted by one or more identical or different radicals from the     group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl,     (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy,     (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkyl which     is optionally substituted by one or more identical or different     radicals from the group consisting of halogen, nitro, cyano,     (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio;     (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl where the     cycloalkyl radical is optionally substituted by (C₁-C₄)-alkyl;     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, cyano-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl,     mono-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl,     di-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl, hydroxy-(C₁-C₄)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl;     phenylsulfonyl which is optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyl; phenylcarbonyl which is     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, nitro, cyano,     (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; and     (C₁-C₄)-alkoxycarbonyl; -   R⁴ is particularly -   preferably selected from the group consisting of H, Me, Et, Pr, cPr,     iPr, Bu, iBu, sBu, tBu, cPen, cHex, CHF₂, CH₂CF₃, Ph, Ph(4-Cl),     CH₂cPr, CH₂cPr(2-Me), CHMecPr, CH₂cBu, CH₂cPen, CH₂cHex, CH₂Ph,     CH₂CH═CH₂, CH₂C≡CH, CHMeC≡CH, CH₂C≡CMe, CH₂OMe, CH₂OEt, CH₂CH₂OH,     CH₂CH₂OMe, CH₂CH₂OEt, CH₂CH₂C(O)Me, CH₂SMe, CH₂SO₂Me, CH₂CN,     CH₂C(O)OMe, CH₂C(O)OEt, CH₂C(O)NH₂, CH₂C(O)NMe₂, CH₂C(O)Me, SO₂Me,     SO₂Ph, C(O)Me, C(O)Ph and C(O)OMe; and -   R⁴ is very particularly -   preferably selected from the group consisting of Me, Et and CHF₂.

A fifth embodiment of the present invention comprises compounds of the formula (I) in which

-   R⁵ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁₋₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino,     (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, cyano-(C₁-C₄)-alkyl,     (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, hydroxy-(C₁-C₂)-alkyl,     hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl;     phenyl which is optionally substituted by one or more identical or     different radicals from the group consisting of halogen, nitro,     cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio;     phenyl-(C₁-C₂)-alkyl which is optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkoxy; phenoxy which is     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, nitro, cyano,     (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio;     (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently     of one another selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups; and -   R⁵ is particularly -   preferably selected from the group consisting of H, F, Cl, Br, I,     CN, Me, Et, CHF₂, CF₃, OCHF₂, OCH₂CF₃, OMe, OEt, OPr, OiPr, OtBu,     SO₂Me, SO₂iPr, 3-oxetanyloxy, OPh, OCH₂CH═CH₂, OCH₂C≡CH, OCH₂CHF₂,     SEt, OCH₂CH₂OCH₃, SMe, OCH₂CH₂CH₂F, OCH(CH₂F)₂, OCH₂CF═CH₂,     OCH(CH₃)CF₃, OCH₂CN, OCH(CH₃)CH₂F, OCH₂CF₂CHF₂ and OCH(CH₃)₂; and -   R⁵ is very particularly -   preferably selected from the group consisting of H, F, Cl, Br, CHF₂,     CF₃, OCHF₂ and OCH₂CF₃.

In the context of the present invention, it is possible to combine the individual preferred, particularly preferred and very particularly preferred meanings of the substituents R¹ to R⁵ as defined in the five embodiments above with one another as desired. This means that the present invention embraces compounds of the formula (I) in which, for example, the substituent R³ has a preferred meaning and the substituents R¹, R², R⁴ and R⁵ have the general meaning or else the substituent R⁴ has a preferred meaning, the substituent R⁵ has a particularly preferred meaning and the substituents R¹ to R³ have a very particularly preferred meaning.

In the context of the present invention, the compounds of the formula (I) also comprise compounds quaternized at a nitrogen atom by a) protonation, b) alkylation or c) oxidation.

If appropriate, the compounds of the formula (I) are able to form salts by forming an adduct with a suitable inorganic or organic acid, such as, for example, HCl, HBr, H₂SO₄ or HNO₃, or else oxalic acid or sulfonic acids, to a basic group, such as, for example, amino or alkylamino. Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, are capable of forming inner salts with groups, such as amino groups, which can be protonated for their part. Salts can also be formed by replacing the hydrogen of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, with a cation suitable in the agrochemical sector. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, especially sodium salts and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts having cations of the formula [NRR′R″R′″]⁺ in which R to R′″ in each case independently are an organic radical, in particular alkyl, aryl, arylalkyl or alkylaryl. In the formula (I) and in all the other formulae of the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless indicated specifically, preference is given for these radicals to the lower carbon skeletons, for example those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms. Alkyl radicals, also in composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl, n-propyl or isopropyl, n-, iso-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl or 1,4-dimethyl-pentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; where at least one double bond or triple bond is present, preferably one double bond or triple bond, respectively. Alkenyl is, for example, vinyl, allyl; 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.

Halogen is fluorine, chlorine, bromine or iodine; haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl and alkynyl, respectively, which are fully or partially substituted by halogen, preferably by fluorine, chlorine or bromine, in particular by fluorine and/or chlorine, examples being monohaloalkyl, perhaloalkyl, CF₃, CHF₂, CH₂F, CF₃CF₂, CH₂FCHCl, CCl₃, CHCl₂, CH₂CH₂Cl; haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, CF₃CF₂O, OCH₂CF₃, and OCH₂CH₂Cl; this correspondingly applies to haloalkenyl and other halogen-substituted radicals.

Optionally substituted aryl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkylthio, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoromethyl- and 2-, 3- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

The definition “substituted by one or more radicals” refers, unless otherwise defined, to one or more identical or different radicals.

The substituents given by way of example (“first substituent level”) can, if they include hydrocarbon-containing fractions, be further substituted therein if desired (“second substituent level”), for example by one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. The term “substituted radical” preferably embraces just one or two substituent levels.

In the case of radicals having carbon atoms, preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C₁-C₄)-alkyl, preferably methyl or ethyl, (C₁-C₄)-haloalkyl, preferably trifluoromethyl, (C₁-C₄)-alkoxy, preferably methoxy or ethoxy, (C₁-C₄)-haloalkoxy, nitro and cyano.

The invention also provides all stereoisomers embraced by formula (I), and mixtures thereof. Such compounds of the formula (I) contain one or more asymmetric carbon atoms (=asymmetrically substituted carbon atoms), or/and asymmetric sulfur atoms in the form of sulfoxides (n=1), which can exist in two enantiomeric forms, or else double bonds, which are not expressly shown in the formula (I). Formula (I) embraces all possible stereoisomers, such as enantiomers, diastereomers and Z and E isomers, defined by their specific spatial form, and these stereoisomers can be obtained by customary methods from mixtures of the stereoisomers or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or the intermediates required in each case for the preparation. These radical definitions can be exchanged for one another as desired, i.e. including combinations between the given preferred ranges.

For the possible combinations of the various substituents of the formula (I) the general principles of the construction of chemical compounds have to be observed, i.e. the formula (I) does not comprise any compounds known to the person skilled in the art as being chemically impossible.

The present invention also provides processes for preparing the compounds of the formula (I) and/or salts thereof.

The compounds of the formula (I) according to the invention can be prepared alternatively by various processes.

In some of the processes below, solvents are used. In this context, “inert solvents” in each case refers to solvents which are inert under the reaction conditions in question, but which do not have to be inert under all reaction conditions.

a.) To prepare optically active sulfoxides of the formula (III) (n=1) or sulfones of the formula (IV) (n=2) in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I),

for example, a thioether of the formula (II)

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I) is oxidized with one equivalent of an oxidizing agent to give the optically active sulfoxides (III) (n=1) or oxidized with two equivalents of an oxidizing agent to give the sulfones (IV) (n=2).

The sulfones of the formula (IV) can also be obtained from the optically active sulfoxides of the formula (III), where the sulfoxides of the formula (III) are oxidized using one equivalent of an oxidizing agent, giving the sulfones of the formula (IV).

The oxidizing agents which can be used for this reaction are not subject to any particular restrictions, it being possible in general to use all oxidizing agents which are capable of oxidizing corresponding sulfur compounds to sulfoxide compounds or sulfone compounds.

Suitable oxidizing agents for preparing the optically active sulfoxides (n=1) are inorganic peroxides such as, for example, hydrogen peroxide, sodium metaperiodate, optionally in the presence of a catalyst such as, for example, ruthenium(III) chloride, organic peroxides such as, for example, tert-butyl hydroperoxide or organic peracids such as peracetic acid or, preferably, 3-chloro-perbenzoic acid. The reaction can be carried out in halogenated hydrocarbons, for example dichloromethane, 1,2-dichloroethane, an alcohol, such as, for example, methanol, or in dimethylformamide, acetonitrile, water or acetic acid, or in a mixture of the solvents mentioned above. The reaction is carried out in a temperature range of between −80 and 120° C., preferably between −20 and 50° C. Such processes are known in the literature and described, for example, in J. Org. Chem., 58 (1993) 2791, J. Org. Chem., 68 (2003) 3849 and J. Heterocyclic Chem., 15 (1978) 1361.

Oxidizing agents suitable for preparing the sulfones (n=2) are, for example, hydrogen peroxide, organic peroxides such as, for example, tert-butyl hydroperoxide or organic peracids such as peracetic acid or, preferably, 3-chloroperbenzoic acid.

The enantioselective synthesis of chiral sulfoxides of the formula (III) in optically enriched or pure form can be carried out from thio compounds of the formula (II) using methods as described, for example, in Chem. Rev., 103 (2003) 3651-3705 and in the literature cited therein, and Adv. Synth. Catal., 347 (2005) 19-31 and in the literature cited therein. In each individual case, the absolute configuration of the product depends on the structure of the optically active catalyst.

Compounds of the formula (III) consist of a mixture of the respective enantiomers (III-S) and (III-R), which are chiral at the sulfoxide function,

where the radicals R¹, R², R³, R⁴, R⁵ have the meaning given above for formula (I).

Suitable for preparing enantiomers of the formula (III) are, in addition to enantioselective syntheses, also customary methods for the separation of racemates (cf. textbooks of stereochemistry).

Racemic mixtures, for example of optically active sulfoxides of the formula (III), can be separated by known processes. Such methods for the separation of racemates are described in textbooks of stereochemistry, for example in “Basic Organic Stereochemistry” (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001; John Wiley & Sons) and “Stereochemistry of Organic Compounds” (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N.; 1994; John Wiley & Sons). Suitable for this purpose are, for example, adduct formation with an optically active auxiliary, separation of the diastereomeric adducts into the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, if appropriate under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers to afford the enantiomers. Suitable for preparative amounts or on an industrial scale are processes such as the crystallization of diastereomeric salts which can be obtained from the compounds (III) using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases. Optically active acids which are suitable for racemate separation by crystallization of diastereomeric salts are, for example, camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids; suitable optically active bases are, for example, quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases.

The crystallizations are then in most cases carried out in aqueous or aqueous-organic solvents, where the diastereomer which is less soluble precipitates first, if appropriate after seeding. One enantiomer of the compound of the formula (III) is then liberated from the precipitated salt, or the other is liberated from the crystals, by acidification or using a base.

Furthermore, racemates can be separated chromatographically using chiral stationary phases. Such enantiomer separations can be carried out in the mg to 100 kg range using preparative HPLC units operated batch-wise or continuously.

The preparation of the thioethers of the formula (II) which serve as starting material for the preparation of the sulfoxides of the formula (III) or the sulfones of the formula (IV) is described below under processes b.), c.), d.), e.), f.), g.) and h.).

b.) To prepare a thioether of the formula (II),

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I), for example, a 2-mercaptooxazole or an oxazole-2(3H)-thione or a salt thereof, preferably an alkali metal or alkaline earth metal salt of the formula (V),

in which R¹, R² have the meanings given above for formula (I), is reacted with a (1H-pyrazol-4-ylmethyl) derivative of the formula (VI)

in which R³, R⁴, R⁵ have the meanings given above for formula (I) and Lg is a leaving group, in the presence of a suitable alkali metal or alkaline earth metal base, for example potassium carbonate or sodium hydride, or an organic base such as, for example, 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), in a suitable solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 and 100° C., and if appropriate under an atmosphere of an inert gas, for example nitrogen.

Analogous reactions for converting 2-mercaptooxazoles or oxazole-2(3H)-thiones or salts thereof have been described in the literature, for example in DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A, Bradsher, C. K.; Jones, W. J. Jr; J. Org. Chem. 32, 2079 (1967).

Instead of the mercapto compounds mentioned or the salt thereof, it is also possible to use mercaptan formers, such as, for example, isothiuronium salts.

Preferred leaving groups Lg are chlorine, bromine, iodine or sulfonate groups, such as methane, trifluoromethane, ethane, benzene or toluenesulfonate.

The 2-mercaptooxazole derivatives or oxazole-2(3H) thiones or the corresponding salts of the 2-mercaptooxazole derivatives or oxazole-2(3H)-thiones of the formula (V) employed in process b.) are known to the person skilled in the art, and some of them are commercially available or can be prepared by processes known to the person skilled in the art, for example as described in a) Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann; b) Houben-Weyl (Methoden der organische Chemie [Methods of Organic Chemistry]), Volume E8a, Hetarene III-part 1, Ed. E. Schaumann; c) Can. J. Chem., Vol. 50, 3082-3083 (1972); d) WO 2003/006442 A.

The (1H-pyrazol-4-ylmethyl) derivatives of the formula (VI) employed in process b.) are known to the person skilled in the art or available commercially or can be prepared by processes known to the person skilled in the art (see, for example: a) Communications de la Faculté des Sciences de l'Université d'Ankara, Series B: Chemistry and Chemical Engineering (1996), 41(1-2), 87-94; b) WO 2004/013106 A; c) WO 2006/024820 A).

c.) Alternatively, the preparation of a thioether of the formula (II),

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I), can take place by reacting an oxazole derivative of the formula (VII),

in which R¹, R² have the meanings given above for formula (I) and Lg′ is a leaving group, suitable leaving groups being inter alia fluorine, chlorine, bromine, iodine, sulfide, sulfoxide or sulfonate groups, with a [(1H-pyrazol-4-ylmethyl)]imidothio-carbamate salt of the formula (VIII)

in which R³, R⁴, R⁵ have the meanings given above for formula (I), Lg is a leaving group, in a one-pot process in the presence of an aqueous alkali metal or alkaline earth metal base.

The reaction is represented in a general manner by the equation below:

The oxazole derivatives of the formula (VII) employed in process c.) are known to the person skilled in the art or available commercially or can be prepared by processes known to the person skilled in the art (as described, for example, in “Science of Synthesis”, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann; DE 26 25 229 A).

The use of imidothiocarbamate salts (isothiuronium salts) in the sense of a one-pot reaction for hydrolyzing the imidothiocarbamate salt (isothiuronium salt) and the reaction of the mercaptan intermediate in an exchange reaction are described in another reaction scheme, for example, in DE 39 42 946, WO 2006/024820 A and WO 2006/037945 A, and under use of phase-transfer catalysis in WO 2007/003294 A and WO 2007/003295 A.

Compounds of the formula (VIII) can be obtained by reacting an alkylating agent of the formula (VI) in which R³, R⁴, R⁵ have the meanings given above for formula (I) and Lg is a leaving group with thiourea.

The preparation of the imidothiocarbamate salts (VIII) by reaction of a (1H-pyrazol-4-yl)methylating agent of the formula (VI) with thiourea is carried out by known processes (such as, for example, by the process described in DD 152557), advantageously by reaction with an equimolar amount of thiourea and optionally in the presence of an alkali metal iodide, for example sodium iodide or potassium iodide, in an inert solvent such as a lower alcohol, for example methanol, ethanol or isopropanol; a hydrocarbon, for example benzene or toluene; a halogenated hydrocarbon, for example dichloromethane or chloroform; or an ether derivative, for example methyl tert-butyl ether, tetrahydrofuran or dioxane, at temperatures between 0 and 150° C., preferably between 20 and 100° C.

In the process according to the invention, the compounds of the imidothiocarbamate salts of the formula (VIII), which in many cases are obtained by crystallization, are generally reacted without any further purification steps under vigorous stirring with equimolar amounts of the oxazole derivatives of the formula (VII) under phase-transfer conditions.

Here, the reaction is advantageously carried out in a two-phase system where, in addition to an aqueous strongly basic alkali metal or alkaline earth metal hydroxide solution, preferably sodium hydroxide or potassium hydroxide, with at least two equivalents of the base, the organic phase is an inert solvent such as tetrahydrofuran, diethyl ether, acetonitrile, pentane, hexane, benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride, nitrobenzene or mixtures of these solvents.

It is also possible to use a slightly subequimolar amount of the respectively more valuable starting material of the formula (VIII) or of the formula (VII).

Suitable phase-transfer catalysts are quaternary ammonium or phosphonium salts and also crown ethers, cryptands or polyethylene glycols. Examples of such catalysts can be found, for example, in W. P. Weber, G. W. Gokel; Phase Transfer Catalysis in Organic Synthesis, Springer-Verlag, Berlin 1977 or E. V. Dehmlow, S. S. Dehmlow, Phase Transfer Catalysis, Second Ed. Verlag Chemie, Weinheim 1983.

The reactants and the catalyst are preferably stirred vigorously at temperatures of from 20 to 100° C. under an atmosphere of protective gas.

The mercaptan intermediate, formed under the reaction conditions, of the formula (IX) in which R³, R⁴, R⁵ have the meaning given above for formula (I)

immediately reacts in situ with the oxazole derivative of the formula (VII).

d.) Alternatively, thioethers of the formula (II) in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I)

can be prepared by reacting an oxazole derivative of the formula (VII)

in which R¹, R² have the meanings given above for formula (I) and Lg′ is a leaving group, suitable leaving groups being chlorine, bromine or methylsulfonyl groups, inter alia, with a (1H-pyrazol-4-ylmethyl)imidothiocarbamate salt (isothiuronium salt) of the formula (VIII)

in which R³, R⁴, R⁵ have the meanings given above for formula (I), Lg is a leaving group, in a one-pot process in the presence of an alkali metal or alkaline earth metal carbonate base and a solvent such as an alcohol.

The reaction is represented in a general manner by the equation below:

Compounds of the formula (VIII) can be obtained by reacting an alkylating agent of the formula (VI) in which R³, R⁴, R⁵ have the meanings given above for formula (I) and Lg is a leaving group with thiourea, as described in process c.) above.

In the process according to the invention, the imidothiocarbamate salts (isothiuronium salts) of the formula (VIII) are generally reacted without any further purification steps under vigorous stirring with a slight excess of the oxazole derivatives of the formula (VII) and with a slight excess of a carbonate base, for example potassium carbonate, sodium carbonate or potassium bicarbonate, or a hydroxide, for example potassium hydroxide, or an alkoxide, for example a sodium alkoxide, in an alcohol, for example ethanol, an ether, for example 1,4-dioxane, tetrahydrofuran, a polar solvent such as, for example, water, dimethylformamide or a mixture of these solvents in a temperature range between 20 and 200° C., preferably between 50 and 150° C., optionally under an atmosphere of an inert gas, for example nitrogen, or in a microwave apparatus.

The imidothiocarbamate salts (isothiuronium salts) of the formula (VIII) can also be reacted further in situ, without isolation.

Here, the reaction is advantageously carried out in an alcohol, preferably ethanol, using at least 1.1 equivalents of the base, preferably potassium carbonate (K₂CO₃).

Such processes are known in the literature and described, for example, in WO 2006/024820 A, WO 2001/012613 A and WO 2006/123088 A.

The oxazole derivatives of the formula (VII) employed in process d.) are known to the person skilled in the art or available commercially, or they can be prepared by processes known to the person skilled in the art [see, for example, Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].

e.) Alternatively, a thioether of the formula (II),

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I), can be prepared by reacting an oxazole derivative of the formula (VII),

in which R¹, R² have the meanings given above for formula (I) and Lg′ is a leaving group, suitable leaving groups LG′ being fluorine, chlorine, bromine or sulfonate groups, inter alia, with a 1H-pyrazol-4-ylmethyl mercaptan of the formula (IX),

in which R³, R⁴, R⁵ have the meaning given above for formula (I), in the presence of an alkali metal or alkaline earth metal base, for example potassium carbonate or sodium hydride, or an organic base, for example preferably 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), optionally in a solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 and 100° C., and optionally under an atmosphere of an inert gas, for example nitrogen.

Some of the processes are known from the literature and are described, for example, in WO 2006/024820 A, WO 2001/012613 A and WO 2006/123088 A.

Nucleophilic substitutions at oxazole derivatives have been described in the literature, for example, in Yamanaka, H.; Ohba, S.; Sakamoto, T.; Heterocycles (1990), 31(6), 1115-27.

The oxazole derivatives of the formula (VII) employed in process e.) are known to the person skilled in the art or available commercially or can be prepared by processes known to the person skilled in the art [see, for example, Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].

The mercaptans of the formula (IX) employed in process e.) are known to the person skilled in the art (see, for example, WO 2004/013106 A) or can be prepared analogously to processes, known to the person skilled in the art, for preparing mercaptans.

f.) Thioethers of the formula (II) in which R², R³, R⁴, R⁵ have the meanings given above for formula (I) and R¹ represents halogen or nitro

can be prepared, for example, by reacting an oxazole derivative of the formula (X),

in which R², R³, R⁴, R⁵ have the meanings given above for formula (I). The reaction is represented in a general manner by the equation below:

The compounds of the formula (X) are treated with a halogenating agent such as, for example, halogen, such as chlorine, bromine, iodine or a halosuccinimide, such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS) or for nitro with a nitrating agent such as, for example, nitrating acid prepared from sulfuric acid and nitric acid, and reacted in suitable solvents such as chlorinated hydrocarbons, for example carbon tetrachloride, dichloromethane, 1,2-dichloroethane or dimethylformamide to give compounds of the formula (II).

The analogous thioether derivatives of the formula (X) employed in process f.) can be prepared by processes known to the person skilled in the art (see, for example: DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A; or by the processes mentioned above under b.), c.), d.), e.).

g.) Thioethers of the formula (II) in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I)

can be prepared, for example, by reacting an oxazole derivative of the formula (XI),

prepared from an oxazole derivative of the formula (V) by reaction with an alkylating agent R¹²Lg′, in which R² has the meanings given above for formula (I); R¹² is preferably (C₁-C₆)-alkyl which is unsubstituted or substituted by one or more identical or different radicals from the halogen group, and particularly preferably is methyl or ethyl, and Lg′ is a leaving group, suitable leaving groups being chlorine, bromine or methylsulfonyl groups, inter alia, in the presence of a strong base and an alkylating agent R¹Lg′, in which R¹ has the meaning given above for formula (I), according to the equation

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I) and Lg or Lg′ is a leaving group, suitable leaving groups being, inter alia, fluorine, chlorine, bromine, iodine or sulfonate groups such as methane-, trifluoromethane-, ethane-, phenyl- or toluenesulfonate, and R¹² preferably has the meaning given above.

The strong base used can be lithium diisopropylamide (LDA), lithium tetramethylpiperidine (LTMP), lithium hexamethyldisilazane (LHMDS), preferably LDA, which can be prepared by processes known to the person skilled in the art. Hexamethylphosphoric triamide (HMPT), for example, can be used as cosolvent.

Inert solvents such as hydrocarbons such as, for example, hexane, heptane, cyclohexane, aromatic hydrocarbons such as, for example, benzene, ethers such as, for example, diethyl ether, methyl tert-butyl ether (MTBE), tetrahydrofuran and dioxane, preferably tetrahydrofuran, serve as solvents. The solvents mentioned above can also be used as mixtures.

In this reaction, the compounds of the formula (XI) and the base or the alkylating agent R¹Lg′ are preferably employed in amount of 0.9 to 1.5 mol of the latter per mole of the former. The reaction is preferably carried out in a temperature range between −90° C. and the boiling point of the solvent. The reaction time is not subject to any restriction; in general, the reactions will have gone to completion after 1 to 24 h.

For preparing the sulfones and sulfoxides of the compounds of the formula (II) in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I), it is possible to use the method given under a).

In particular in the case that R¹ is fluorine, preference is given to using reagents for electrophilic fluorination, such as, for example, 1-chloromethyl-4-fluoro-1,4-diazabi-cyclo[2,2,2]octane bistetrafluoroborate (F-TEDA-BF4, SelectFluor™), N-fluorobenzenesulfonimide (NFBS or NFSi), N-fluoro-o-benzenedisulfonimide (NFOBS), 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (NFTh, AccuFluor™) and others, as described in “Modern Fluoroorganic Chemistry”, 2004, Wiley-VCH Verlag, Ed. P. Kirsch.

The 2-mercaptooxazole derivatives or oxazole-2(3H)-thiones or the corresponding salts of the 2-mercaptooxazole derivatives or oxazole-2(3H)-thione derivatives of the formula (V) employed in process g.) are known to the person skilled in the art or available commercially or can be prepared by processes known to the person skilled in the art, for example as described in Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann.

Analogously to processes known to the person skilled in the art, it is possible to deprotonate oxazole derivatives (XI) regioselectively in the 5-position. Analogous reactions using an alkyl base such as buthyllithium have been described in the literature, for example in Boger, D. L. et al; J. Med. Chem. (2007) 50 (33), 1058-1068 and Molinski, T. F. et al. J. Org. Chem. (1998) 63, 551-555, and using tort-butyllithium and a copper salt in Marino, J. P.; Nguyen, N. Tet. Lett. (2003) 44, 7395-7398 and the literature cited therein.

The oxazole derivatives of the formula (XI) employed in process g.) can be prepared, for example, according to process b.) by reacting a 2-mercaptooxazole derivative or oxazole-2(3H)-thione derivative of the formula (V) with an alkylating agent R¹²Lg′ or according to processes known to the person skilled in the art [see, for example, Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann], or they are commercially available.

The compounds of the formula (XIII) mentioned in process g.) can be prepared from the compounds of the formula (XII) by oxidation according to process a) above or by processes known to the person skilled in the art. In turn, the compounds of the formula (XIII) can be reacted by the above process c.) or d.) with (1H-pyrazol-4-ylmethyl) imidothiocarbamate salts (VIII) or with (1H-pyrazol-4-ylmethyl) mercaptans of the formula (IX) according to the above process e.) to give compounds of type (II).

h.) Thioethers of the formula (II) in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I)

can also be prepared, for example, by reacting a (1H-pyrazol-4-ylmethyl) disulfide derivative of the formula (XV) with 2-aminooxazoles of the formula (XIV) and a diazotizing agent, as shown in the equation below

in which R¹, R², R³, R⁴, R⁵ have the meanings given above for formula (I).

The (1H-pyrazol-4-ylmethyl) disulfides of the formula (XV) are reacted with a diazotizing agent and a 2-aminooxazole derivative of the formula (XIV) in a suitable solvent to give compounds of the formula (II).

Suitable solvents are reaction-inert solvents such as, for example, hydrocarbons, such as hexane, heptane, cyclohexane, aromatic hydrocarbons such as benzene, chlorobenzene, toluene, xylene, halogenated hydrocarbons such as, for example, dichloromethane, dichloroethane, chloroform and carbon tetrachloride, esters such as, for example, ethyl acetate and methyl acetate, ethers such as, for example, diethyl ether, methyl tert-butyl ether, dioxane, nitriles such as acetonitrile, alcohols such as, for example, methanol, ethanol, isopropyl alcohol, amides such as, for example, N,N-dimethylformamide, and sulfoxides such as, for example, dimethyl sulfoxide.

The diazotizing agent may, for example, be a nitrite ester such as isoamyl nitrite or a nitrite salt such as, for example, sodium nitrite. The molar ratios can be chosen as desired; equimolar amounts of heteroarylalkyl disulfides and diazotizing agents are preferred. The reaction is preferably carried out at a temperature between −20° C. and the boiling point of the chosen solvent and is gone to completion after a period of from 0.1 to 40 hours.

The diazotization of a 2-aminooxazole derivative of the formula (XIV) is described, for example, in Hodgetts, K. J.; Kershaw, M. T. Org. Lett. (2002), 4(17), 2905-2907.

The oxazole derivatives of the formula (XIV) employed in process h.) are known to the person skilled in the art or available commercially, or they can be prepared by processes known to the person skilled in the art (see Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann).

The 1H-pyrazol-4-ylmethyl disulfides of the formula (XV) can be prepared by processes known to the person skilled in the art, for example as in Gladysz, J. A., Wong, V. K., Jick, B. S.; Tetrahedron (1979) 35, 2329.

Preferred leaving groups Lg are halogens, for example chlorine, bromine, iodine, or alkyl- or arylsulfonyl groups, such as methyl-, ethyl-, phenyl- or tolylsulfonyl, or a haloalkylsulfonyl group, such as trifluoromethyl, or nitro; however, preference is given to chlorine and methylsulfonyl.

Preferred leaving groups Lg′ are halogens, for example chlorine, bromine, iodine, or alkyl- or arylsulfonyl groups, such as methyl-, ethyl-, phenyl- or tolylsulfonyl, or a haloalkylsulfonyl group, such as trifluoromethyl, or nitro; however, preference is given to chlorine and methylsulfonyl.

A preferred group R¹² is (C₁-C₆)-alkyl which is unsubstituted or optionally substituted by one or more identical or different radicals from the halogen group, particularly preferably methyl or ethyl.

The present compounds of the formula (III)

consist of a mixture of the respective chiral entantiomers (III-S) and (III-R):

Thus, they have a chiral sulfur atom which, in the structure shown above, is illustrated by the marker (R/S). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have either an (R) configuration or an (S) configuration.

The present invention encompasses compounds of the formula (III) both with (S) and with (R) configuration, i.e. the present invention encompasses the compounds of the formula (III) in which the sulfur atom in question has

-   (1) an (R) configuration; or -   (2) an (S) configuration.

In addition, the scope of the present invention also encompasses

-   (3) any mixtures of compounds of the formula (III) having an (R)     configuration (compounds of the formula (III-(R)) with compounds of     the formula (III) having an (S) configuration (compounds of the     formula (III-(S)).

The present invention embraces racemic compounds of the formula (III), i.e. where the compounds of the formula (III) having the (S) configuration (compounds of the formula (III-S)) are, compared to the (R) configuration (compounds of the formula (III-R)), present as a 1:1 mixture (stereochemical purity 50%).

However, within the context of the present invention, preference is also given to compounds of the formula (III) having (S) configuration (compounds of the formula (III-S)) as compared to the (R) configuration (compounds of the formula (III-R)) having a stereochemical purity of in general from more than 50% to 100%, preferably from 60 to 100%, in particular from 80 to 100%, very particularly from 90 to 100%, especially from 95 to 100%, where the particular (S) compound is preferably present with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) compound in question.

In the context of the present invention, preference is furthermore also given to compounds of the formula (III) having the (R) configuration (compounds of the formula (III-R)) as compared to the (S) configuration (compounds of the formula (III-R)) having a stereochemical purity of in general from more than 50% to 100%, preferably from 60 to 100%, in particular from 80 to 100%, very particularly from 90 to 100%, especially from 95 to 100%, where the respective (R) compound is preferably present in an enantioselectivity of in each case more than 50% ee, preferably from 60 to 100% ee, in particular from 80 to 100% ee, very particularly from 90 to 100% ee, most preferably from 95 to 100% ee, based on the total content of the respective (S) compound.

Accordingly, the present invention also relates to compounds of the formula (III) in which the stereochemical configuration at the sulfur atom (S) marked by (*) is of a stereochemical purity of from 60 to 100% (S), preferably from 80 to 100% (S), in particular from 90 to 100% (S), very particularly from 95 to 100% (S).

Depending on the type and attachment of the substituents, the compounds of the formula (III) may contain further centers of chirality in addition to the sulfur atom marked (*) in formula (III), in which case they are then present as stereoisomers. The formula (III) encompasses all possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers. If, for example, one or more alkenyl groups are present, there may be diastereomers (Z and E isomers). If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers. Stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. Accordingly, the invention also relates to all stereoisomers embraced by the formula (III) but not shown in their specific stereoform, and to their mixtures.

If, for example, one or more alkenyl groups are present, there may be diastereomers (Z and E isomers).

If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers.

Such stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. Accordingly, the invention also relates to all stereoisomers embraced by the formula (I) but not shown in their specific stereoform, and to their mixtures.

In the context of the present invention, acid addition salts of the compounds of the formula (I) can also be used. The following acids are suitable for preparing the acid addition salts of the compounds of the formula (I): hydrohalic acids, such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, or lactic acid, and also sulfonic acids, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid. The acid addition compounds of the formula (I) can be obtained in a simple manner by the customary methods for forming salts, for example by dissolving a compound of the formula (I) in a suitable organic solvent, such as, for example, methanol, acetone, methylene chloride or benzene, and adding the acid at temperatures of from 0 to 100° C., and they can be isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.

The base addition salts of the compounds of the formula (I) are preferably prepared in inert polar solvents, such as, for example, water, methanol or acetone, at temperatures of from 0 to 100° C. Examples of bases which are suitable for the preparation of the salts according to the invention are alkali metal carbonates, such as potassium carbonate, alkali metal hydroxides and alkaline earth metal hydroxides, for example NaOH or KOH, alkali metal hydrides and alkaline earth metal hydrides, for example NaH, alkali metal alkoxides and alkaline earth metal alkoxides, for example sodium methoxide or potassium tert-butoxide, or ammonia, ethanolamine or quaternary ammonium hydroxide of the formula [NRR′R″R′″]⁺OH⁻.

Collections of compounds of the formula (I) and/or their salts which can be synthesized in accordance with the abovementioned reactions can also be prepared in a parallelized manner, which can be effected manually or in a partly or fully automated manner. Here, it is possible for example to automate the procedure of the reaction, the work-up or the purification of the products or intermediates. In total, this is understood as meaning a procedure as described for example by D. Tiebes in Combinatorial Chemistry—Synthesis, Analysis, Screening (Editor Günther Jung), Wiley 1999, on pages 1 to 34.

A number of commercially available apparatuses can be used for the parallelized reaction procedure and work-up, for example Calpyso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA, or reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MuItiPROBE Automated Workstations from Perkin Elmar, Waltham, Mass. 02451, USA. Chromatographic apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA, are available, inter alia, for the parallelized purification of compounds of the formula (I) and their salts or of intermediates generated in the course of the preparation.

The apparatuses listed lead to a modular procedure in which the individual passes are automated, but manual operations must be carried out between the passes. This can be circumvented by the use of partly or fully integrated automation systems, where the relevant automation modules are operated by, for example, robots. Such automation systems can be obtained for example from Caliper, Hopkinton, Mass. 01748, USA.

The performance of individual, or a plurality of, synthesis steps can be aided by the use of polymer-supported reagents/scavenger resins. The specialist literature describes a series of experimental protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

Besides the methods described herein, the preparation of compounds of the formula (I) and their salts can be effected fully or in part by solid-phase-supported methods. For this purpose, individual intermediates, or all intermediates, of the synthesis or of a synthesis adapted to the relevant procedure are bound to a synthesis resin. Solid-phase-supported synthesis methods are described sufficiently in the specialist literature, for example Barry A. Bunin in “The Combinatorial Index”, Academic Press, 1998 and Combinatorial Chemistry—Synthesis, Analysis, Screening (Editor Günther Jung), Wiley, 1999. The use of solid-phase-supported synthesis methods permits a series of protocols known from the literature, which, again, can be carried out manually or in an automated manner. For example, the reactions can be carried out by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, Calif. 92064, USA.

Carrying out individual or a plurality of synthesis steps, both on a solid and in the liquid phase, can be aided by the use of microwave technology. A series of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (Editors C. O. Kappe and A. Stadler), Wiley, 2005.

The preparation in accordance with the processes described herein generates compounds of the formula (I) and their salts in the form of substance collections, which are referred to as libraries. The present invention also relates to libraries which comprise at least two compounds of the formula (I) and their salts.

On account of their herbicidal and plant growth regulatory properties, the active compounds can also be used for controlling harmful plants in crops of known plants or genetically modified plants which are yet to be developed. As a rule, the transgenic plants are distinguished by particularly advantageous properties, for example by resistances to certain pesticides, primarily certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with respect to quantity, quality, storability, composition and specific ingredients. For example, transgenic plants with increased starch content or modified quality of the starch or those with a different fatty acid composition of the harvested material are known. Further particular properties can lie in a tolerance or resistance to abiotic stress factors, for example heat, cold, drought, salt and ultraviolet radiation.

Preference is given to using the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful plants and ornamental plants, for example of cereals such as wheat, barley, rye, oats, millet, rice, manioc and corn, or else crops of sugarbeet, cotton, soybean, rapeseed, potatoes, tomatoes, peas and other vegetable varieties.

Preferably, the compounds of the formula (I) can be used as herbicides in crops of useful plants which are resistant to, or have been rendered genetically resistant to, the phytotoxic effects of the herbicides.

Conventional ways of producing new plants which have modified properties compared to existing plants consist, for example, in classic cultivation methods and the generation of mutants. Alternatively, new plants with modified properties can be produced using genetic engineering methods (see e.g. EP 0221044, EP 0131624). For example, in several cases the following have been described

-   -   genetic modifications of crop plants for the purpose of         modifying the starch synthesized in the plants (e.g. WO         92/011376 A, WO 92/014827 A, WO 91/019806 A),     -   transgenic crop plants which are resistant to certain herbicides         of the glufosinate type (cf. e.g. EP 0 242 236 A, EP 0 242         246 A) or of the glyphosate type (WO 92/000377 A) or of the         sulfonylurea type (EP 0 257 993 A, U.S. Pat. No. 5,013,659) or         to combinations or mixtures of these herbicides through “gene         stacking”, such as transgenic crop plants e.g. corn or soybean         with the tradename or the name Optimum™ GAT™ (glyphosate ALS         tolerant),     -   transgenic crop plants, for example cotton, with the ability to         produce Bacillus thuringiensis toxins (Bt toxins) which make the         plants resistant to certain pests (EP 0 142 924 A, EP 0 193 259         A),     -   transgenic crop plants with a modified fatty acid composition         (WO 91/013972 A),     -   genetically modified crop plants with new ingredients or         secondary substances, e.g. new phytoalexins, which bring about         increased resistance to disease (EP 0 309 862 A, EP 0 464 461         A),     -   genetically modified plants with reduced photorespiration which         have higher yields and higher stress tolerance (EP 0 305 398 A),     -   transgenic crop plants which produce pharmaceutically or         diagnostically important proteins (“molecular pharming”),     -   transgenic crop plants distinguished by higher yields or better         quality,     -   transgenic crop plants distinguished by combinations e.g. of the         aforementioned new properties (“gene stacking”).

Numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known in principle; see e.g. I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, “Trends in Plant Science” 1 (1996) 423-431.

For genetic manipulations of this kind, nucleic acid molecules which permit a mutagenesis or a sequence modification by recombination of DNA sequences can be introduced into plasmids. For example, with the help of standard methods, it is possible to carry out base exchanges, to remove part sequences or to add natural or synthetic sequences. For joining the DNA fragments to one another, adaptors or linkers may be added to the fragments, see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene and Klone [Genes and Clones]”, VCH Weinheim 2nd edition, 1996.

The preparation of plant cells with reduced activity of a gene product can be achieved, for example, through the expression of at least one corresponding antisense-RNA, a sense-RNA to achieve a cosuppression effect or the expression of at least one correspondingly constructed ribozyme which specifically cleaves transcripts of the aforementioned gene product.

To this end, it is possible to use firstly DNA molecules which encompass the entire coding sequence of a gene product including any flanking sequences which may be present, and also DNA molecules which only encompass parts of the coding sequence, it being necessary for these parts to be long enough to bring about an antisense effect in the cells. Also possible is the use of DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not entirely identical thereto.

During the expression of nucleic acid molecules in plants, the synthesized protein can be localized in any compartment of the plant cell. However, in order to achieve localization in a certain compartment, it is possible, for example, to link the coding region with DNA sequences which ensure localization in a certain compartment. Sequences of this type are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The expression of the nucleic acid molecules can also take place in the organelles of the plant cells.

The transgenic plant cells can be regenerated by known techniques to give whole plants. In principle, the transgenic plants may be plants of any desired plant species, i.e. either monocotyledonous or dicotyledonous plants.

Transgenic plants are thus obtainable which have modified properties as a result of overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=foreign) genes or gene sequences.

It is preferred to employ the compounds (I) according to the invention in transgenic crops which are resistant to growth regulators such as, for example, 2,4 D, dicamba, or against herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or against herbicides from the group of the sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active compounds or against any combinations of these active compounds.

The compounds according to the invention can be particularly preferably used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. The compounds according to the invention can very particularly preferably be used in transgenic crop plants such as e.g. corn or soybean with the tradename or the name Optimum™ GAT™ (glyphosate ALS tolerant).

When the active compounds according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.

The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations. The invention therefore also provides herbicides and plant growth-regulating compositions which comprise the compounds according to the invention.

The compounds of the formula (I) can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation assistants, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to prepare combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a tank mix.

Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltauride. To prepare the wettable powders, the active herbicidal ingredients are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation assistants.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

Dusting products are obtained by grinding the active compound with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants, as have, for example, already been listed above for the other formulation types.

Granules can be produced either by spraying the active compound onto adsorptive granulated inert material or by applying active compound concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils, onto the surface of carriers such as sand, kaolinites or of granulated inert material. It is also possible to granulate suitable active compounds in the manner customary for the production of fertilizer granules—if desired in a mixture with fertilizers.

Water-dispersible granules are prepared generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the preparation of pan, fluidized bed, extruder and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 if; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, p. 8-57.

For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations contain generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).

In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight; the remainder to 100% by weight consists of customary formulation constituents. In the case of emulsifiable concentrates, the active compound concentration may be from about 1 to 90% by weight, preferably from 5 to 80% by weight. Dust-type formulations contain from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In water-dispersible granules, the active compound content depends partly on whether the active compound is present in solid or liquid form and which granulation assistants, fillers, etc. are used. In the granules dispersible in water, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the specified active compound formulations optionally comprise the adhesives, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, antifreezes and solvents, fillers, carriers and colorants, antifoams, evaporation inhibitors and agents which influence the pH and the viscosity that are customary in each case.

The compounds of the formula (I) or their salts can be used as such or combined in the form of their preparations (formulations) with other pesticidally active substances, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, e.g. as ready mix or as tank mixes.

Combination partners which can be used for the compounds of the formula (I) according to the invention in mixture formulations or in the tank mix are, for example, known active compounds which are based on an inhibition of, for example, acetolactate synthase, acetyl-coenzyme-A-carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and literature cited therein. Known herbicides or plant growth regulators which can be combined with the compounds according to the invention are, for example, the following active compounds (the compounds are designated either with the “common name” in accordance with the International Organization for Standardization (ISO) or with the chemical name or with the code number) and always encompass all of the application forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers. Here, by way of example, one and sometimes also more application forms are specified:

acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron-methyl, bentazone, benzfendizone, benzobicyclon, benzofenap, benzosfluor, benzoylprop, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromuron, buminafos, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorazifop, chlorazifop-butyl, chlorbromuron, chlorbufam, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlormequat chloride, chlornitrofen, chlorophthalim, chlorthal-dimethyl, chlorotoluron, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cyclanilide, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine, cyprazole, 2,4-D, 2,4-DB, daimuron/dymron, dalapon, daminozide, dazomet, n-decanol, desmedipham, desmetryn, detosyl-pyrazolate (DTP), diallate, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimethachior, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPIC, esprocarb, ethaifluralin, ethametsulfuron-methyl, ethephon, ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-5331, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr, flufenpyr-ethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone, fluorochloridone, fluoroxypyr, fluoroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamine, furyloxyfen, gibberellic acid, glufosinate, L-glufosinate, L-glufosinate-ammonium, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HNPC-9908, HOK-201, HW-02, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, inabenfide, indanofan, indoleacetic acid (IAA), 4-indol-3-ylbutyric acid (IBA), iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, isocarbamid, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, KUH-043, KUH-071, karbutilate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidide, mepiquat chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, methazole, methoxyphenone, methyldymron, 1-methylcyclopropene, methyl isothiocyanate, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monocarbamide, monocarbamide dihydrogensulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011, naproanilide, napropamide, naptalam, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrophenolat-sodium (isomer mixture), nitrofluorfen, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paclobutrazole, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, pirifenop, pirifenop-butyl, pretilachlor, primisulfuron, primisulfuron-methyl, probenazole, profluazole, procyazine, prodiamine, prifluraline, profoxydim, prohexadione, prohexadione-calcium, prohydrojasmone, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochior, propoxycarbazone, propoxycarbazone-sodium, propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynachlor, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, secbumeton, sethoxydim, siduron, simazine, simetryn, SN-106279, sulcotrione, sulfallate (CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, TH-547, thenylchlor, thiafluamide, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, topramezone, tralkoxydim, triallate, triasulfuron, triaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, tsitodef, uniconazole, uniconazole-P, vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 and the following compounds

Of particular interest is the selective control of harmful plants in crops of useful plants and ornamental plants. Although the compounds of the formula (I) according to the invention already have very good to adequate selectivity in many crops, it is in principle possible, in some crops and primarily also in the case of mixtures with other herbicides which are less selective, for phytotoxicities on the crop plants to occur. In this connection, combinations of compounds of the formula (I) according to the invention are of particular interest which comprise the compounds of the formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners which are used in an antidotically effective content reduce the phytotoxic side-effects of the herbicides/pesticides used, e.g. in economically important crops such as cereals (wheat, barley, rye, corn, rice, millet), sugarbeet, sugarcane, rapeseed, cotton and soybean, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I) alone or else in their combinations with further pesticides:

-   S1) Compounds of the Formula (S1),

-   where the symbols and indices have the following meanings: -   n_(A) is a natural number from 0 to 5, preferably 0 to 3; -   R_(A) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or     (C₁-C₄)-haloalkyl; -   W_(A) is an unsubstituted or substituted divalent heterocyclic     radical from the group of the partially unsaturated or aromatic     five-ring heterocycles having 1 to 3 heteroring atoms from the group     consisting of N and O, where at least one N atom and at most one O     atom is present in the ring, preferably a radical from the group     (W_(A) ¹) to (W_(A) ⁴),

-   m_(A) is 0 or 1; -   R_(A) ² is OR_(A) ³, SR_(A) ³ or NR_(A) ³R_(A) ⁴ or a saturated or     unsaturated 3- to 7-membered heterocycle with at least one N atom     and up to 3 heteroatoms, preferably from the group consisting of O     and S, which is bonded to the carbonyl group in (S1) via the N atom     and is unsubstituted or substituted by radicals from the group     consisting of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or optionally     substituted phenyl, preferably a radical of the formula OR_(A) ³,     NHR_(A) ⁴ or N(CH₃)₂, in particular of the formula OR_(A) ³; -   R_(A) ³ is hydrogen or an unsubstituted or substituted aliphatic     hydrocarbon radical, preferably having in total 1 to 18 carbon     atoms; -   R_(A) ⁴ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or substituted or     unsubstituted phenyl; -   R_(A) ⁵ is H, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₈)-alkyl, cyano or COOR_(A) ⁹, in which R_(A) ⁹     is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, (C₁-C₆)-hydroxyalkyl,     (C₃-C₁₂)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl; -   R_(A) ⁶, R_(A) ⁷, R_(A) ⁸ are identical or different, hydrogen,     (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₃-C₁₂)-cycloalkyl or substituted     or unsubstituted phenyl; -   preferably: -   a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type     (S1^(a)), preferably compounds such as     -   1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic         acid, ethyl         1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate         (S1-1) (“mefenpyr-diethyl”), and related compounds, as described         in WO-A-91/07874; -   b) derivatives of dichlorophenylpyrazolecarboxylic acid (S1^(b)),     preferably corn-pounds such as ethyl     1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl     1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3),     ethyl     1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate     (S1-4) and related compounds, as described in EP-A-333 131 and     EP-A-269 806; -   c) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1^(c)),     preferably compounds such as ethyl     1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl     1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related     compounds, as described, for example, in EP-A-268554; -   d) compounds of the triazolecarboxylic acid type (S1^(d)),     preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl     1-(2,4-dichlorophenyl)-5-trichloro-methyl-(1H)-1,2,4-triazole-3-carboxylate     (S1-7), and related compounds, as described in EP-A-174 562 and     EP-A-346 620; -   e) compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic     acid type or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid     type (S1^(e)), preferably compounds such as ethyl     5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl     5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds,     as described in WO-A-91/08202, or     5,5-diphenyl-2-isoxazoline-carboxylic acid (S1-10) or ethyl     5,5-diphenyl-2-isoxazolinecarboxylate (S1-11) (“isoxadifen-ethyl”)     or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S1-12) or of the     ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate type     (S1-13), as described in the patent application WO-A-95/07897. -   S2) Quinoline Derivatives of the Formula (S2),

-   where the symbols and indices have the following meanings: -   R_(B) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or     (C₁-C₄)-haloalkyl; -   n_(B) is a natural number from 0 to 5, preferably 0 to 3; -   R_(B) ² is OR_(B) ³, SR_(B) ³ or NR_(B) ³R_(B) ⁴ or a saturated or     unsaturated 3- to 7-membered heterocycle having at least one N atom     and up to 3 heteroatoms, preferably from the group consisting of O     and S, which is joined to the carbonyl group in (S2) via the N atom     and is unsubstituted or substituted by radicals from the group     consisting of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or optionally     substituted phenyl, preferably a radical of the formula OR_(B) ³,     NHR_(B) ⁴ or N(CH₃)₂, in particular of the formula OR_(B) ³; -   R_(B) ³ is hydrogen or an unsubstituted or substituted aliphatic     hydrocarbon radical, preferably having in total 1 to 18 carbon     atoms; -   R_(B) ⁴ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or substituted or     unsubstituted phenyl; -   T_(B) is a (C₁ or C₂)-alkanediyl chain which is unsubstituted or     substituted by one or two (C₁-C₄)-alkyl radicals or by     [(C₁-C₃)-alkoxy]carbonyl; -   preferably: -   a) compounds of the 8-quinolinoxyacetic acid type (S2^(a)),     preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate     (“cloquintocet-mexyl”) (S2-1), 1,3-dimethylbut-1-yl     (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl     (5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl     (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl     (5-chloro-8-quinolinoxy)acetate (S2-5), methyl     (5-chloro-8-quinolinoxy)acetate (S2-6), allyl     (5-chloro-8-quinolinoxy)acetate (S2-7),     2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate     (S2-8), 2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and     related compounds, as described in EP-A-86 750, EP-A-94 349 and     EP-A-191 736 or EP-A-0 492 366, and also     (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts,     for example its lithium, sodium, potassium, calcium, magnesium,     aluminum, iron, ammonium, quaternary ammonium, sulfonium or     phosphonium salts, as described in WO-A-2002/34048; -   b) compounds of the (5-chloro-8-quinolinoxy)malonic acid type     (S2^(b)), preferably compounds such as diethyl     (5-chloro-8-quinolinoxy)malonate, diallyl     (5-chloro-8-quinolinoxy)malonate, methyl ethyl     (5-chloro-8-quinolinoxy)-malonate and related compounds, as     described in EP-A-0 582 198. -   S3) Compounds of the Formula (S3)

-   where the symbols and indices have the following meanings: -   R_(C) ¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,     (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably dichloromethyl; -   R_(C) ², R_(C) ³ are identical or different, hydrogen,     (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,     (C₂-C₄)-haloalkenyl, (C₁-C₄)-alkylcarbamoyl-(C₁-C₄)-alkyl,     (C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, dioxolanyl-(C₁-C₄)-alkyl, thiazolyl,     furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted     phenyl, or R_(C) ² and R_(C) ³ form together a substituted or     unsubstituted heterocyclic ring, preferably an oxazolidine,     thiazolidine, piperidine, morpholine, hexahydropyrimidine or     benzoxazine ring; -   preferably:     -   active compounds of the dichloroacetamide type, which are often         used as pre-emergence safeners (soil-acting safeners), such as,         for example, -   “dichlormid” (N,N-diallyl-2,2-dichloroacetamide) (S3-1), -   “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from     Stauffer (S3-2), -   “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from     Stauffer (S3-3), -   “benoxacor”     (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), -   “PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide)     from PPG Industries (S3-5), -   “DKA-24” (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide)     from Sagro-Chem (S3-6), -   “AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane)     from Nitrokemia or Monsanto (S3-7), -   “TI-35” (1-dichloroacetylazepane) from TRI-Chemical RT (S3-8), -   “diclonon” (dicyclonone) or “BAS145138” or “LAB145138” (S3-9)     (3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane)     from BASF, -   “furilazole” or “MON 13900”     ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyl-oxazolidine)     (S3-10); and also its (R)-isomer (S3-11). -   S4) N-Acylsulfonamides of the Formula (S4) and their Salts,

-   in which the symbols and indices have the following meanings: -   X_(D) is CH or N; -   R_(D) ¹ is CO—NR_(D) ⁵R_(D) ⁶ or NHCO—R_(D) ⁷; -   R_(D) ² is halogen, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, nitro,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl; -   R_(D) ³ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or     (C₂-C₄)-alkynyl; -   R_(D) ⁴ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,     cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkyl-sulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylcarbonyl; -   R_(D) ⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,     (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₅-C₆)-cycloalkenyl, phenyl or 3-     to 6-membered heterocyclyl comprising v_(D) heteroatoms from the     group consisting of nitrogen, oxygen and sulfur, where the seven     last-mentioned radicals are substituted by v_(D) substituents from     the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,     (C₁-C₂)-alkylsulfinyl, (C₁-C₂)-alkylsulfonyl, (C₃-C₆)-cycloalkyl,     (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylcarbonyl and phenyl and, in the     case of cyclic radicals, also (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl; -   R_(D) ⁶ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl or     (C₂-C₆)-alkynyl, where the three last-mentioned radicals are     substituted by v_(D) radicals from the group consisting of halogen,     hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and (C₁-C₄)-alkylthio, or -   R_(D) ⁶ and R_(D) ⁶ together with the nitrogen atom carrying them     form a pyrrolidinyl or piperidinyl radical; -   R_(D) ⁷ is hydrogen, (C₁-C₄)-alkylamino, di-(C₁-C₄)-alkylamino,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where the 2 last-mentioned     radicals are substituted by v_(D) substituents from the group     consisting of halogen, (C₁-C₄)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also (C_(r)     C₄)-alkyl and (C₁-C₄)-haloalkyl; -   n_(D) is 0, 1 or 2; -   m_(D) is 1 or 2; -   v_(D) is 0, 1, 2 or 3;     -   of which preference is given to compounds of the         N-acylsulfonamide type, for example of the following formula         (S4^(a)), which are known, for example, from WO-A-97/45016

-   -   in which

-   R_(D) ⁷ is (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where the 2     last-mentioned radicals are substituted by v_(D) substituents from     the group consisting of halogen, (C₁-C₄)-alkoxy, (C₁-C₆)-haloalkoxy     and (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also     (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl;

-   R_(D) ⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃;

-   m_(D) is 1 or 2;

-   v_(D) is 0, 1, 2 or 3;

-   and     -   acylsulfamoylbenzamides, e.g. of the following formula (S4^(b)),         which are known, for example, from WO-A-99/16744,

-   e.g. those in which -   R_(D) ⁵=cyclopropyl and (R_(D) ⁴)=2-OMe (“cyprosulfamide”, S4-1), -   R_(D) ⁵=cyclopropyl and (R_(D) ⁴)=5-Cl-2-OMe (S4-2), -   R_(D) ⁵=ethyl and (R_(D) ⁴)=2-OMe (S4-3), -   R_(D) ⁵=isopropyl and (R_(D) ⁴)=5-Cl-2-OMe (S4-4) and -   R_(D) ⁵=isopropyl and (R_(D) ⁴)=2-OMe (S4-5), -   and     -   compounds of the N-acylsulfamoylphenylurea type of the formula         (S4^(c)), which are known, for example, from EP-A-365484,

-   in which -   R_(D) ⁸ and R_(D) ⁹, independently of one another, are hydrogen,     (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl, -   R_(D) ⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃ -   m_(D) is 1 or 2; -   for example -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, -   1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea. -   S5) Active compounds from the class of hydroxyaromatics and     aromatic-aliphatic carboxylic acid derivatives (S5), e.g. ethyl     3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid,     3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid,     4-fluorosalicyclic acid, 2-hydroxycinnamic acid,     2,4-dichlorocinnamic acid, as described in WO-A-2004/084631,     WO-A-2005/015994, WO-A-2005/016001. -   S6) Active compounds from the class of the     1,2-dihydroquinoxalin-2-ones (S6), e.g.     1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,     1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione,     1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydro-quinoxalin-2-one     hydrochloride,     1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,     as described in WO-A-2005/112630. -   S7) Compounds of the Formula (S7), as Described in WO-A-1998/38856

-   in which the symbols and the indices have the following meanings: -   R_(E) ¹, R_(E) ² independently of one another are halogen,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl,     (C₁-C₄)-alkylamino, di-(C₁-C₄)-alkylamino, nitro; -   A_(E) is COOR_(E) ³ or COSR_(E) ⁴ -   R_(E) ³, R_(E) ⁴ independently of one another are hydrogen,     (C₁-C₄)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₄)-alkynyl, cyanoalkyl,     (C₁-C₄)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl,     pyridinylalkyl and alkylammonium, -   n_(E) ¹ is 0 or 1 -   n_(E) ², n_(E) ³ independently of one another are 0, 1 or 2, -   preferably:     -   diphenylmethoxyacetic acid,     -   ethyl diphenylmethoxyacetate,     -   methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1). -   S8) Compounds of the Formula (S8), as Described in WO-A-98/27049

-   in which -   X_(F) is CH or N, -   n_(F) if X_(F)═N, is an integer from 0 to 4 and     -   if X_(F)═CH, is an integer from 0 to 5, -   R_(F) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, nitro, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl, optionally     substituted phenyl, optionally substituted phenoxy, -   R_(F) ² is hydrogen or (C₁-C₄)-alkyl, -   R_(F) ³ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₄)-alkenyl,     (C₂-C₄)-alkynyl, or aryl, where each of the aforementioned     C-containing radicals is unsubstituted or substituted by one or     more, preferably up to three, identical or different radicals from     the group consisting of halogen and alkoxy, or salts thereof, -   preferably compounds in which -   X_(F) is CH, -   n_(F) is an integer from 0 to 2, -   R_(F) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, -   R_(F) ² is hydrogen or (C₁-C₄)-alkyl, -   R_(F) ³ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₄)-alkenyl,     (C₂-C₄)-alkynyl, or aryl, where each of the aforementioned     C-containing radicals is unsubstituted or substituted by one or     more, preferably up to three, identical or different radicals from     the group consisting of halogen and alkoxy, or salts thereof. -   S9) Active Compounds from the Class of the     3-(5-tetrazolylcarbonyl)-2-quinolones (S9), e.g.     -   1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone         (CAS Reg. No. 219479-18-2),         1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone         (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020. -   S10) Compounds of the Formulae (S10^(a)) or (S10^(b))     -   as described in WO-A-2007/023719 and WO-A-2007/023764

-   in which -   R_(G) ¹ is halogen, (C₁-C₄)-alkyl, methoxy, nitro, cyano, CF₃, OCF₃ -   Y_(G), Z_(G) independently of one another are O or S, -   n_(G) is an integer from 0 to 4, -   R_(G) ² is (C₁-C₁₆)-alkyl, (C₂-C₆)-alkenyl, (C₃-C₆)-cycloalkyl,     aryl; benzyl, halobenzyl, -   R_(G) ³ is hydrogen or (C₁-C₆)-alkyl. -   S11) Active Compounds of the Oxyimino Compound Type (S11), which are     Known as Seed Dressings, Such as, for Example,     -   “oxabetrinil”         ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1),         which is known as seed dressing safener for millet against         metolachlor damage,     -   “fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone         O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as         seed dressing safener for millet against metolachlor damage, and     -   “cyometrinil” or “CGA-43089”         ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is         known as seed dressing safener for millet against metolachlor         damage. -   S12) Active compounds from the class of the isothiochromanones     (S12), such as, for example, methyl     [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg.     No. 205121-04-6) (S12-1) and related compounds from WO-A-1998/13361. -   S13) One or More Compounds from Group (S13):     -   “naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride)         (S13-1), which is known as seed dressing safener for corn         against thiocarbamate herbicide damage,     -   “fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is         known as safener for pretilachlor in sown rice,     -   “flurazole” (benzyl         2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3),         which is known as seed dressing safener for millet against         alachlor and metolachlor damage,     -   “CL 304415” (CAS Reg. No. 31541-57-8)     -   (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid), (S13-4)         from American Cyanamid, which is known as safener for corn         against imidazolinone damage,     -   “MG 191” (CAS Reg. No. 96420-72-3)         (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from         Nitrokemia, which is known as safener for corn,     -   “MG-838” (CAS Reg. No. 133993-74-5)     -   (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate)         (S13-6) from Nitrokemia,     -   “disulfoton” (O,O-diethyl S-2-ethylthioethyl phosphorodithioate)         (S13-7),     -   “dietholate” (O,O-diethyl O-phenyl phosphorothioate) (S13-8),     -   “mephenate” (4-chlorophenyl methylcarbamate) (S13-9). -   S14) Active compounds which, besides a herbicidal effect against     harmful plants, also have safener effect on crop plants such as     rice, such as, for example,     -   “dimepiperate” or “MY-93” (S-1-methyl-1-phenylethyl         piperidine-1-carbothioate), which is known as safener for rice         against molinate herbicide damage,     -   “daimuron” or “SK 23”         (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as         safener for rice against imazosulfuron herbicide damage,     -   “cumyluron”=“JC-940”         (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, see         JP-A-60087254), which is known as safener for rice against some         herbicide damage,     -   “methoxyphenone” or “NK 049”         (3,3′-dimethyl-4-methoxybenzophenone), which is known as safener         for rice against some herbicide damage,     -   “CSB” (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai,         (CAS Reg. No. 54091-06-4), which is known as safener against         some herbicide damage in rice. -   S15) Active compounds which are primarily used as herbicides, but     also have safener effect on crop plants, for example -   (2,4-dichlorophenoxy)acetic acid (2,4-D), -   (4-chlorophenoxy)acetic acid, -   (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), -   4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), -   (4-chloro-o-tolyloxy)acetic acid (MCPA), -   4-(4-chloro-o-tolyloxy)butyric acid, -   4-(4-chlorophenoxy)butyric acid, -   3,6-dichloro-2-methoxybenzoic acid (dicamba), -   1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate     (lactidichlor-ethyl).

Some of the safeners are already known as herbicides and thus, besides the herbicidal effect in respect of harmful plants, at the same time also develop a protective effect in respect of the crop plants.

The weight ratios of herbicide (mixture) to safener generally depend on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200:1 to 1:200, preferably 100:1 to 1:100, in particular 20:1 to 1:20. The safeners can be formulated analogously to the compounds of the formula (I) or mixtures thereof with further herbicides/pesticides and can be provided and applied as ready mix or tank mix with the herbicides.

For use, the formulations present in standard commercial form are, if appropriate, diluted in the usual manner, e.g. in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, soil and scatter granules, and also sprayable solutions are usually no longer diluted with further inert substances prior to use.

The required application rate of the compounds of the formula (I) varies inter alia with the external conditions such as temperature, humidity, the type of herbicide used. It can fluctuate within wide limits, e.g. between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha.

The present invention is illustrated in more detail by reference to the examples below, although these do not limit the invention in any way.

SYNTHESIS EXAMPLES

A number of synthesis examples of compounds of the formula (I) or their salts are described in an exemplary manner below.

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (Ex. 49)

1,3-Oxazole-2(3H)-thione (2.960 g, 29 mmol; prepared as described in WO 2003/006442 A) is initially charged in 50 ml of acetonitrile. With ice-bath cooling, 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU, 4.81 ml, 32 mmol) is added dropwise. The mixture is stirred at 25° C. for 30 minutes. A solution of 4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazole (9.045 g, 29 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred at 25° C. for a further 4 hours and allowed to stand overnight. For work-up, the reaction mixture is added to water and extracted twice with dichloromethane, and the extracts are then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptan:ethyl acetate, gradient 10:0 to 7:3). This gives 7.6 g of product (74.9% of theory).

NMR (CDCl₃, 400 MHz): 3.82 (s, 3H, CH₃); 4.32 (s, 2H, SCH₂); 6.75 (t, 1H, OCHF₂); 7.11 (br s, 1H); 7.68 (br s, 1H).

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole (Ex. 50)

Under an atmosphere of argon, 2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (2.00 g, 6 mmol) is initially charged in 333 ml of dichloromethane. With stirring and ice-cooling, 3-chloroperbenzoic acid (1.362 g, 6 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at 0° C. for a further 6 hours. For work-up, the reaction mixture is extracted twice with 2-molar sodium hydroxide solution and then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptane:ethyl acetate, gradient 10:0 to 6:4). This gives 1.98 g of product (89.7% of theory).

NMR (CDCl₃, 400 MHz): 3.86 (s, 3H, CH₃); 4.36 (d, 1H, S(O)CH₂); 4.49 (d, 1H, S(O)CH₂); 6.97 (dd, 1H, OCHF₂); 7.39 (br s, 1H); 7.93 (br s, 1H).

2-[(S)-{[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-oxazole (Ex. 2285) and 2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-oxazole (Ex. 3041)

The racemic 2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole (0.5 g, 99% pure) obtained is separated into the enantiomers by preparative chiral HPLC (column: Chiralpak® IC; mobile phase: n-heptane/2-propanol 80:20; flow rate: 90 ml/min; column temperature: 25° C.). This gives 0.2 g (40% of theory) of 2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-oxazole (R_(t)=8.129 min, [α]^(D)=−126.1°) and 0.2 g (40% of theory) of 2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-oxazole (R_(t)=10.286 min, [α]^(D)=+123.3°).

The absolute configuration of 2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-oxazole was confirmed by X-ray structural analysis.

Retention times (R_(t), in minutes) and enantiomeric ratios (ee) of chiral compounds were determined by analytical chiral HPLC [Chiralpak® IC column (250×4.6 mm, particle size 10 μm), temperature 25° C., flow rate 1 ml/min, n-heptane/2-propanol 80:20 v/v].

Racemates or enantiomeric mixtures were separated into the respective enantiomers by preparative chiral HPLC [Chiralpak® IC column (250×50 mm, particle size 20 μm), temperature 25° C., flow rate 90 ml/min, n-heptane/2-propanol 80:20 v/v].

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole (Ex. 51)

Under an atmosphere of argon, 2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (0.30 g, 1 mmol) is initially charged in 50 ml of dichloromethane. With stirring and ice-cooling, 3-chloroperbenzoic acid (0.449 g, 2 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at 25° C. for a further 3 hours and allowed to stand overnight. A further 100 mg of 3-chloroperbenzoic acid are added, and stirring at 25° C. is continued for 4 hours. For work-up, the reaction mixture is washed twice with 2-molar sodium hydroxide solution, then with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified by preparative HPLC (reverse phase). This gives 0.097 g of product (28% of theory).

NMR (CDCl₃, 400 MHz): 3.87 (s, 3H, CH₃); 4.59 (s, 2H, S(O)₂CH₂); 6.84 (t, 1H, OCHF₂); 7.4 (br s, 1H); 7.89 (br s, 1H).

5-Bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (Ex. 787) a) Preparation of 2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole [according to Can. J. Chem., Vol. 50, 3082-3083 (1972)]

Under an atmosphere of argon, dihydroxyfumaric acid (5.00 g, 34 mmol) is added a little at a time to water (20 ml) at a temperature of 60° C. (evolution of gas). The mixture is stirred at 60° C. until the evolution of gas has ceased (about 1 h; solution 1). Potassium thiocyanate (3.282 g, 34 mmol) is initially charged in ethanol (25 ml). At 0° C., concentrated hydrochloric acid (4 ml, 4.76 g, 48 mmol) is added dropwise, and the mixture is stirred at 25° C. for 1 hour. The precipitated potassium chloride formed is filtered off with suction, the filtrate is slowly added dropwise to solution 1 at room temperature and the mixture is then stirred at reflux for another 12 hours. The reaction solution is concentrated, and acetonitrile (50 ml) is added to the aqueous residue. Initially potassium carbonate (7.00 g, 51 mmol) and then 4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazole (5.218 g, 17 mmol) are added, and the mixture is stirred at 60° C. for a further 7 hours. For work-up, the reaction mixture is added to water and extracted twice with ethyl acetate, and the extracts are then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptane:ethyl acetate, gradient 10:0 to 7:3). This gives 3.09 g of product (26.4% of theory).

b) Preparation of 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (1.24 g, 4 mmol) is initially charged in 20 ml of dimethylformamide. N-Bromosuccinimide (0.892 g, 5 mmol) is then added a little at a time with stirring. The mixture is stirred at 40° C. for a further 6 hours. For work-up, the reaction mixture is added to water and extracted twice with dichloromethane, and the extracts are then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptane:ethyl acetate, gradient 10:0 to 7:3). This gives 0.70 g of product (43.2% of theory).

NMR (CDCl₃, 400 MHz): 3.81 (s, 3H, CH₃); 4.28 (s, 2H, SCH₂); 6.71 (t, 1H, OCHF₂); 6.98 (s, 1H).

5-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (Ex. 541)

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (1.02 g, 3 mmol) is initially charged in 15 ml of dimethylformamide. N-Chlorosuccinimide (0.550 g, 4 mmol) is then added a little at a time with stirring. The mixture is stirred at 40° C. for a further 4 hours. For work-up, the reaction mixture is added to water and extracted twice with dichloromethane, and the extracts are then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptane:ethyl acetate, gradient 10:0 to 7:3). This gives 0.45 g of product (35.9% of theory).

NMR (CDCl₃, 400 MHz): 3.80 (s, 3H, CH₃); 4.28 (s, 2H, SCH₂); 6.69 (t, 1H, OCHF₂); 6.88 (s, 1H).

5-Iodo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (Ex. 1033)

2-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole (0.700 g, 2 mmol) is initially charged in 10 ml of dimethylformamide. N-Iodosuccinimide (0.750 g, 3.3 mmol) is then added a little at a time with stirring. The mixture is stirred at 40° C. for a further 16 hours. For work-up, the reaction mixture is added to water and extracted twice with dichloromethane, and the extracts are then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified chromatographically (heptane:ethyl acetate, gradient 10:0 to 8:2). This gives 0.25 g of product (24.5% of theory).

NMR (CDCl₃, 400 MHz): 3.80 (s, 3H, CH₃); 4.29 (s, 2H, SCH₂); 6.70 (t, 1H, OCHF₂); 7.11 (s, 1H).

2-({[5-(Chloro)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1, oxazole (Ex. 34) a) Preparation of 2-(methylsulfonyl)-1,3-oxazole

Under an atmosphere of protective gas, 1,3-oxazole-2(3H)-thione (1.00 g, 10 mmol; prepared as described in WO 2003/006442 A) is initially charged in 20 ml of acetonitrile. Iodomethane (1.544 g, 0.677 ml, 11 mmol) is added dropwise, then potassium carbonate (1.503 ml, 11 mmol) is added. The mixture is stirred at 25° C. for 6 hours. For work-up, the reaction mixture is added to water and extracted twice with dichloromethane (100 ml), and the extract is then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and directly reacted further. With stirring and ice-cooling, 3-chloro-perbenzoic acid (5.100 g, 23 mmol, 77% pure) is then added a little at a time to this solution in dichloromethane, and the mixture is stirred at 25° C. for a further 6 hours and then allowed to stand overnight. For work-up, the reaction mixture is washed twice with 2-molar sodium hydroxide solution, then with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. This gives 0.820 g of product (50.7% of theory).

NMR (CDCl₃, 400 MHz): 3.35 (s, 3H, CH₃); 7.38 (br s, 1H); 7.88 (br s, 1H).

b) Preparation of 2-({[5-(chloro)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

[5-Chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl imidothiocarbamate hydrobromide (1.934 g, 5 mmol) is added to a vigorously stirred mixture consisting of 50 ml of toluene and 50% strength aqueous sodium hydroxide solution (21 g), and the mixture is stirred vigorously for a further 1.5 hours. Tetra-n-butylammonium bromide (0.494 g, 2 mmol) and 2-(methylsulfonyl)-1,3-oxazole (0.805 g, 5 mmol) are then added, and the mixture is stirred vigorously at 25° C. for a further 6 hours. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. This gives 1.290 g of product (75.2% of theory).

NMR (CDCl₃, 400 MHz): 3.89 (s, 3H, CH₃); 4.33 (s, 2H, SCH₂); 7.12 (br s, 1H); 7.68 (br s, 1H).

The compounds described in Tables 1-3 below are obtained in accordance with or analogously to the synthesis examples described above.

In the tables:

Me=methyl Et=ethyl Ph=phenyl Pr=n-propyl cPr=cyclopropyl iPr=isopropyl tBu=tert-butyl cPen=cyclopentyl

TABLE 1 Compounds of the formula (I) ( I )

Ex. No. R¹ R² R³ R⁴ R⁵ n 1. H H CF₃ Ph Cl 0 2. H H CF₃ Ph Cl 1 3. H H CF₃ Ph Cl 2 4. H H CF₃ tBu Cl 0 5. H H CF₃ tBu Cl 1 6. H H CF₃ tBu Cl 2 7. H H CF₃ CHF₂ Cl 0 8. H H CF₃ CHF₂ Cl 1 9. H H CF₃ CHF₂ Cl 2 10. H H Cl CHF₂ CF₃ 0 11. H H Cl CHF₂ CF₃ 1 12. H H Cl CHF₂ CF₃ 2 13. H H CF₃ Me OMe 0 14. H H CF₃ Me OMe 1 15. H H CF₃ Me OMe 2 16. H H CF₃ Me CN 0 17. H H CF₃ Me CN 1 18. H H CF₃ Me CN 2 19. H H Cl Et Cl 0 20. H H Cl Et Cl 1 21. H H Cl Et Cl 2 22. H H CHF₂ Me Cl 0 23. H H CHF₂ Me Cl 1 24. H H CHF₂ Me Cl 2 25. H H Me Me Me 0 26. H H Me Me Me 1 27. H H Me Me Me 2 28. H H Me Me Cl 0 29. H H Me Me Cl 1 30. H H Me Me Cl 2 31. H H Cl Me Cl 0 32. H H Cl Me Cl 1 33. H H Cl Me Cl 2 34. H H CF₃ Me Cl 0 35. H H CF₃ Me Cl 1 36. H H CF₃ Me Cl 2 37. H H Cl Me CF₃ 0 38. H H Cl Me CF₃ 1 39. H H Cl Me CF₃ 2 40. H H CF₃ Me F 0 41. H H CF₃ Me F 1 42. H H CF₃ Me F 2 43. H H OMe Me CF₃ 0 44. H H OMe Me CF₃ 1 45. H H OMe Me CF₃ 2 46. H H CF₃ Me OEt 0 47. H H CF₃ Me OEt 1 48. H H CF₃ Me OEt 2 49. H H CF₃ Me OCHF₂ 0 50. H H CF₃ Me OCHF₂ 1 51. H H CF₃ Me OCHF₂ 2 52. H H OCHF₂ Me CF₃ 0 53. H H OCHF₂ Me CF₃ 1 54. H H OCHF₂ Me CF₃ 2 55. H H CF₃ Me OCH₂CHF₂ 0 56. H H CF₃ Me OCH₂CHF₂ 1 57. H H CF₃ Me OCH₂CHF₂ 2 58. H H CF₃ Me OCH₂CF₃ 0 59. H H CF₃ Me OCH₂CF₃ 1 60. H H CF₃ Me OCH₂CF₃ 2 61. H H CF₃ Me OCH₂CN 0 62. H H CF₃ Me OCH₂CN 1 63. H H CF₃ Me OCH₂CN 2 64. H H CF₃ Me SO₂Me 0 65. H H CF₃ Me SO₂Me 1 66. H H CF₃ Me SO₂Me 2 67. H H CF₃ Me SEt 0 68. H H CF₃ Me SEt 1 69. H H CF₃ Me SEt 2 70. H H CF₃ Me Me 0 71. H H CF₃ Me Me 1 72. H H CF₃ Me Me 2 73. H H CF₃ Me Et 0 74. H H CF₃ Me Et 1 75. H H CF₃ Me Et 2 76. H H CF₃ Et Cl 0 77. H H CF₃ Et Cl 1 78. H H CF₃ Et Cl 2 79. H H Cl Et CF₃ 0 80. H H Cl Et CF₃ 1 81. H H Cl Et CF₃ 2 82. H H CF₃ iPr Cl 0 83. H H CF₃ iPr Cl 1 84. H H CF₃ iPr Cl 2 85. H H Cl iPr CF₃ 0 86. H H Cl iPr CF₃ 1 87. H H Cl iPr CF₃ 2 88. H H CF₃ tBu Cl 0 89. H H CF₃ tBu Cl 1 90. H H CF₃ tBu Cl 2 91. H H Cl tBu CF₃ 0 92. H H Cl tBu CF₃ 1 93. H H Cl tBu CF₃ 2 94. H H CF₃ cPen Cl 0 95. H H CF₃ cPen Cl 1 96. H H CF₃ cPen Cl 2 97. H H Cl cPen CF₃ 0 98. H H Cl cPen CF₃ 1 99. H H Cl cPen CF₃ 2 100. H H CF₃ CH₂cPr Cl 0 101. H H CF₃ CH₂cPr Cl 1 102. H H CF₃ CH₂cPr Cl 2 103. H H Cl CH₂cPr CF₃ 0 104. H H Cl CH₂cPr CF₃ 1 105. H H Cl CH₂cPr CF₃ 2 106. H H CF₃ CH₂CH═CH₂ Cl 0 107. H H CF₃ CH₂CH═CH₂ Cl 1 108. H H CF₃ CH₂CH═CH₂ Cl 2 109. H H Cl CH₂CH═CH₂ CF₃ 0 110. H H Cl CH₂CH═CH₂ CF₃ 1 111. H H Cl CH₂CH═CH₂ CF₃ 2 112. H H CF₃ CHF₂ OMe 0 113. H H CF₃ CHF₂ OMe 1 114. H H CF₃ CHF₂ OMe 2 115. H H OMe CHF₂ CF₃ 0 116. H H OMe CHF₂ CF₃ 1 117. H H OMe CHF₂ CF₃ 2 118. H H CF₃ CH₂CF₃ Cl 0 119. H H CF₃ CH₂CF₃ Cl 1 120. H H CF₃ CH₂CF₃ Cl 2 121. H H Cl CH₂CF₃ CF₃ 0 122. H H Cl CH₂CF₃ CF₃ 1 123. H H Cl CH₂CF₃ CF₃ 2 124. H H CF₃ CH₂OMe Cl 0 125. H H CF₃ CH₂OMe Cl 1 126. H H CF₃ CH₂OMe Cl 2 127. H H Cl CH₂OMe CF₃ 0 128. H H Cl CH₂OMe CF₃ 1 129. H H Cl CH₂OMe CF₃ 2 130. H H CF₃ CH₂CN Cl 0 131. H H CF₃ CH₂CN Cl 1 132. H H CF₃ CH₂CN Cl 2 133. H H Me Ph Me 0 134. H H Me Ph Me 1 135. H H Me Ph Me 2 136. H H Me Ph Cl 0 137. H H Me Ph Cl 1 138. H H Me Ph Cl 2 139. H H Et Ph Cl 0 140. H H Et Ph Cl 1 141. H H Et Ph Cl 2 142. H H Pr Ph Cl 0 143. H H Pr Ph Cl 1 144. H H Pr Ph Cl 2 145. H H iPr Ph Cl 0 146. H H iPr Ph Cl 1 147. H H iPr Ph Cl 2 148. H H CF₃ Ph Cl 0 149. H H CF₃ Ph Cl 1 150. H H CF₃ Ph Cl 2 151. H H CF₃ Ph Me 0 152. H H CF₃ Ph Me 1 153. H H CF₃ Ph Me 2 154. H H CF₃ Ph CF₃ 0 155. H H CF₃ Ph CF₃ 1 156. H H CF₃ Ph CF₃ 2 157. H H CF₃ Ph F 0 158. H H CF₃ Ph F 1 159. H H CF₃ Ph F 2 160. H H CF₃ Ph OMe 0 161. H H CF₃ Ph OMe 1 162. H H CF₃ Ph OMe 2 163. H H CF₃ Ph OEt 0 164. H H CF₃ Ph OEt 1 165. H H CF₃ Ph OEt 2 166. H H CF₃ Ph OCHF₂ 0 167. H H CF₃ Ph OCHF₂ 1 168. H H CF₃ Ph OCHF₂ 2 169. H H CF₃ Ph CN 0 170. H H CF₃ Ph CN 1 171. H H CF₃ Ph CN 2 172. H H CF₃ Ph(4-Cl) Cl 0 173. H H CF₃ Ph(4-Cl) Cl 1 174. H H CF₃ Ph(4-Cl) Cl 2 175. H H Me Me OCH₂CF₃ 0 176. H H Me Me OCH₂CF₃ 1 177. H H Me Me OCH₂CF₃ 2 178. H H CF₃ Me

0 179. H H CF₃ Me

1 180. H H CF₃ Me

2 181. H H CF₃ Me H 0 182. H H CF₃ Me H 1 183. H H CF₃ Me H 2 184. H H CF₃ Me OCH₂CH₂OMe 0 185. H H CF₃ Me OCH₂CH₂OMe 1 186. H H CF₃ Me OCH₂CH₂OMe 2 187. H H CF₃ Me SMe 0 188. H H CF₃ Me SMe 1 189. H H CF₃ Me SMe 2 190. H H CF₃ Me OCH₂CH₂CH₂F 0 191. H H CF₃ Me OCH₂CH₂CH₂F 1 192. H H CF₃ Me OCH₂CH₂CH₂F 2 193. H H CF₃ Me OCH(CH₂F)₂ 0 194. H H CF₃ Me OCH(CH₂F)₂ 1 195. H H CF₃ Me OCH(CH₂F)₂ 2 196. H H CF₃ Me OCH₂CF₂CHF₂ 0 197. H H CF₃ Me OCH₂CF₂CHF₂ 1 198. H H CF₃ Me OCH₂CF₂CHF₂ 2 199. H H CF₃ Me OCH₂CF═CH₂ 0 200. H H CF₃ Me OCH₂CF═CH₂ 1 201. H H CF₃ Me OCH₂CF═CH₂ 2 202. H H CF₃ Me OCH(Me)CF₃ 0 203. H H CF₃ Me OCH(Me)CF₃ 1 204. H H CF₃ Me OCH(Me)CF₃ 2 205. H H CF₃ Me OCH(Me)CH₂F 0 206. H H CF₃ Me OCH(Me)CH₂F 1 207. H H CF₃ Me OCH(Me)CH₂F 2 208. H H OCH₂CF₃ Me CF₃ 0 209. H H OCH₂CF₃ Me CF₃ 1 210. H H OCH₂CF₃ Me CF₃ 2 211. H H OCH₂CF₃ Me CHF₂ 0 212. H H OCH₂CF₃ Me CHF₂ 1 213. H H OCH₂CF₃ Me CHF₂ 2 214. H H CHF₂ Me CHF₂ 0 215. H H CHF₂ Me CHF₂ 1 216. H H CHF₂ Me CHF₂ 2 217. H H CF₃ Me CHF₂ 0 218. H H CF₃ Me CHF₂ 1 219. H H CF₃ Me CHF₂ 2 220. H H Cl Me OCHF₂ 0 221. H H Cl Me OCHF₂ 1 222. H H Cl Me OCHF₂ 2 223. H H Br Me OCHF₂ 0 224. H H Br Me OCHF₂ 1 225. H H Br Me OCHF₂ 2 226. H H Br Me CF₃ 0 227. H H Br Me CF₃ 1 228. H H Br Me CF₃ 2 229. H H CF₃ Me CF₃ 0 230. H H CF₃ Me CF₃ 1 231. H H CF₃ Me CF₃ 2 232. H H CHF₂ Me CF₃ 0 233. H H CHF₂ Me CF₃ 1 234. H H CHF₂ Me CF₃ 2 235. H H CF₂CF₃ Me CF₃ 0 236. H H CF₂CF₃ Me CF₃ 1 237. H H CF₂CF₃ Me CF₃ 2 238. H H CF₃ Me CF₂CF₃ 0 239. H H CF₃ Me CF₂CF₃ 1 240. H H CF₃ Me CF₂CF₃ 2 241. H H CHF₂ Me OCH₂CF₃ 0 242. H H CHF₂ Me OCH₂CF₃ 1 243. H H CHF₂ Me OCH₂CF₃ 2 244. H H CHF₂ Me OCHF₂ 0 245. H H CHF₂ Me OCHF₂ 1 246. H H CHF₂ Me OCHF₂ 2 247. F H CF₃ Ph Cl 0 248. F H CF₃ Ph Cl 1 249. F H CF₃ Ph Cl 2 250. F H CF₃ tBu Cl 0 251. F H CF₃ tBu Cl 1 252. F H CF₃ tBu Cl 2 253. F H CF₃ CHF₂ Cl 0 254. F H CF₃ CHF₂ Cl 1 255. F H CF₃ CHF₂ Cl 2 256. F H Cl CHF₂ CF₃ 0 257. F H Cl CHF₂ CF₃ 1 258. F H Cl CHF₂ CF₃ 2 259. F H CF₃ Me OMe 0 260. F H CF₃ Me OMe 1 261. F H CF₃ Me OMe 2 262. F H CF₃ Me CN 0 263. F H CF₃ Me CN 1 264. F H CF₃ Me CN 2 265. F H Cl Et Cl 0 266. F H Cl Et Cl 1 267. F H Cl Et Cl 2 268. F H CHF₂ Me Cl 0 269. F H CHF₂ Me Cl 1 270. F H CHF₂ Me Cl 2 271. F H Me Me Me 0 272. F H Me Me Me 1 273. F H Me Me Me 2 274. F H Me Me Cl 0 275. F H Me Me Cl 1 276. F H Me Me Cl 2 277. F H Cl Me Cl 0 278. F H Cl Me Cl 1 279. F H Cl Me Cl 2 280. F H CF₃ Me Cl 0 281. F H CF₃ Me Cl 1 282. F H CF₃ Me Cl 2 283. F H Cl Me CF₃ 0 284. F H Cl Me CF₃ 1 285. F H Cl Me CF₃ 2 286. F H CF₃ Me F 0 287. F H CF₃ Me F 1 288. F H CF₃ Me F 2 289. F H OMe Me CF₃ 0 290. F H OMe Me CF₃ 1 291. F H OMe Me CF₃ 2 292. F H CF₃ Me OEt 0 293. F H CF₃ Me OEt 1 294. F H CF₃ Me OEt 2 295. F H CF₃ Me OCHF₂ 0 296. F H CF₃ Me OCHF₂ 1 297. F H CF₃ Me OCHF₂ 2 298. F H OCHF₂ Me CF₃ 0 299. F H OCHF₂ Me CF₃ 1 300. F H OCHF₂ Me CF₃ 2 301. F H CF₃ Me OCH₂CHF₂ 0 302. F H CF₃ Me OCH₂CHF₂ 1 303. F H CF₃ Me OCH₂CHF₂ 2 304. F H CF₃ Me OCH₂CF₃ 0 305. F H CF₃ Me OCH₂CF₃ 1 306. F H CF₃ Me OCH₂CF₃ 2 307. F H CF₃ Me OCH₂CN 0 308. F H CF₃ Me OCH₂CN 1 309. F H CF₃ Me OCH₂CN 2 310. F H CF₃ Me SO₂Me 0 311. F H CF₃ Me SO₂Me 1 312. F H CF₃ Me SO₂Me 2 313. F H CF₃ Me SEt 0 314. F H CF₃ Me SEt 1 315. F H CF₃ Me SEt 2 316. F H CF₃ Me Me 0 317. F H CF₃ Me Me 1 318. F H CF₃ Me Me 2 319. F H CF₃ Me Et 0 320. F H CF₃ Me Et 1 321. F H CF₃ Me Et 2 322. F H CF₃ Et Cl 0 323. F H CF₃ Et Cl 1 324. F H CF₃ Et Cl 2 325. F H Cl Et CF₃ 0 326. F H Cl Et CF₃ 1 327. F H Cl Et CF₃ 2 328. F H CF₃ iPr Cl 0 329. F H CF₃ iPr Cl 1 330. F H CF₃ iPr Cl 2 331. F H Cl iPr CF₃ 0 332. F H Cl iPr CF₃ 1 333. F H Cl iPr CF₃ 2 334. F H CF₃ tBu Cl 0 335. F H CF₃ tBu Cl 1 336. F H CF₃ tBu Cl 2 337. F H Cl tBu CF₃ 0 338. F H Cl tBu CF₃ 1 339. F H Cl tBu CF₃ 2 340. F H CF₃ cPen Cl 0 341. F H CF₃ cPen Cl 1 342. F H CF₃ cPen Cl 2 343. F H Cl cPen CF₃ 0 344. F H Cl cPen CF₃ 1 345. F H Cl cPen CF₃ 2 346. F H CF₃ CH₂cPr Cl 0 347. F H CF₃ CH₂cPr Cl 1 348. F H CF₃ CH₂cPr Cl 2 349. F H Cl CH₂cPr CF₃ 0 350. F H Cl CH₂cPr CF₃ 1 351. F H Cl CH₂cPr CF₃ 2 352. F H CF₃ CH₂CH═CH₂ Cl 0 353. F H CF₃ CH₂CH═CH₂ Cl 1 354. F H CF₃ CH₂CH═CH₂ Cl 2 355. F H Cl CH₂CH═CH₂ CF₃ 0 356. F H Cl CH₂CH═CH₂ CF₃ 1 357. F H Cl CH₂CH═CH₂ CF₃ 2 358. F H CF₃ CHF₂ OMe 0 359. F H CF₃ CHF₂ OMe 1 360. F H CF₃ CHF₂ OMe 2 361. F H OMe CHF₂ CF₃ 0 362. F H OMe CHF₂ CF₃ 1 363. F H OMe CHF₂ CF₃ 2 364. F H CF₃ CH₂CF₃ Cl 0 365. F H CF₃ CH₂CF₃ Cl 1 366. F H CF₃ CH₂CF₃ Cl 2 367. F H Cl CH₂CF₃ CF₃ 0 368. F H Cl CH₂CF₃ CF₃ 1 369. F H Cl CH₂CF₃ CF₃ 2 370. F H CF₃ CH₂OMe Cl 0 371. F H CF₃ CH₂OMe Cl 1 372. F H CF₃ CH₂OMe Cl 2 373. F H Cl CH₂OMe CF₃ 0 374. F H Cl CH₂OMe CF₃ 1 375. F H Cl CH₂OMe CF₃ 2 376. F H CF₃ CH₂CN Cl 0 377. F H CF₃ CH₂CN Cl 1 378. F H CF₃ CH₂CN Cl 2 379. F H Me Ph Me 0 380. F H Me Ph Me 1 381. F H Me Ph Me 2 382. F H Me Ph Cl 0 383. F H Me Ph Cl 1 384. F H Me Ph Cl 2 385. F H Et Ph Cl 0 386. F H Et Ph Cl 1 387. F H Et Ph Cl 2 388. F H Pr Ph Cl 0 389. F H Pr Ph Cl 1 390. F H Pr Ph Cl 2 391. F H iPr Ph Cl 0 392. F H iPr Ph Cl 1 393. F H iPr Ph Cl 2 394. F H CF₃ Ph Cl 0 395. F H CF₃ Ph Cl 1 396. F H CF₃ Ph Cl 2 397. F H CF₃ Ph Me 0 398. F H CF₃ Ph Me 1 399. F H CF₃ Ph Me 2 400. F H CF₃ Ph CF₃ 0 401. F H CF₃ Ph CF₃ 1 402. F H CF₃ Ph CF₃ 2 403. F H CF₃ Ph F 0 404. F H CF₃ Ph F 1 405. F H CF₃ Ph F 2 406. F H CF₃ Ph OMe 0 407. F H CF₃ Ph OMe 1 408. F H CF₃ Ph OMe 2 409. F H CF₃ Ph OEt 0 410. F H CF₃ Ph OEt 1 411. F H CF₃ Ph OEt 2 412. F H CF₃ Ph OCHF₂ 0 413. F H CF₃ Ph OCHF₂ 1 414. F H CF₃ Ph OCHF₂ 2 415. F H CF₃ Ph CN 0 416. F H CF₃ Ph CN 1 417. F H CF₃ Ph CN 2 418. F H CF₃ Ph(4-Cl) Cl 0 419. F H CF₃ Ph(4-Cl) Cl 1 420. F H CF₃ Ph(4-Cl) Cl 2 421. F H Me Me OCH₂CF₃ 0 422. F H Me Me OCH₂CF₃ 1 423. F H Me Me OCH₂CF₃ 2 424. F H CF₃ Me

0 425. F H CF₃ Me

1 426. F H CF₃ Me

2 427. F H CF₃ Me H 0 428. F H CF₃ Me H 1 429. F H CF₃ Me H 2 430. F H CF₃ Me OCH₂CH₂OMe 0 431. F H CF₃ Me OCH₂CH₂OMe 1 432. F H CF₃ Me OCH₂CH₂OMe 2 433. F H CF₃ Me SMe 0 434. F H CF₃ Me SMe 1 435. F H CF₃ Me SMe 2 436. F H CF₃ Me OCH₂CH₂CH₂F 0 437. F H CF₃ Me OCH₂CH₂CH₂F 1 438. F H CF₃ Me OCH₂CH₂CH₂F 2 439. F H CF₃ Me OCH(CH₂F)₂ 0 440. F H CF₃ Me OCH(CH₂F)₂ 1 441. F H CF₃ Me OCH(CH₂F)₂ 2 442. F H CF₃ Me OCH₂CF₂CHF₂ 0 443. F H CF₃ Me OCH₂CF₂CHF₂ 1 444. F H CF₃ Me OCH₂CF₂CHF₂ 2 445. F H CF₃ Me OCH₂CF═CH₂ 0 446. F H CF₃ Me OCH₂CF═CH₂ 1 447. F H CF₃ Me OCH₂CF═CH₂ 2 448. F H CF₃ Me OCH(Me)CF₃ 0 449. F H CF₃ Me OCH(Me)CF₃ 1 450. F H CF₃ Me OCH(Me)CF₃ 2 451. F H CF₃ Me OCH(Me)CH₂F 0 452. F H CF₃ Me OCH(Me)CH₂F 1 453. F H CF₃ Me OCH(Me)CH₂F 2 454. F H OCH₂CF₃ Me CF₃ 0 455. F H OCH₂CF₃ Me CF₃ 1 456. F H OCH₂CF₃ Me CF₃ 2 457. F H OCH₂CF₃ Me CHF₂ 0 458. F H OCH₂CF₃ Me CHF₂ 1 459. F H OCH₂CF₃ Me CHF₂ 2 460. F H CHF₂ Me CHF₂ 0 461. F H CHF₂ Me CHF₂ 1 462. F H CHF₂ Me CHF₂ 2 463. F H CF₃ Me CHF₂ 0 464. F H CF₃ Me CHF₂ 1 465. F H CF₃ Me CHF₂ 2 466. F H Cl Me OCHF₂ 0 467. F H Cl Me OCHF₂ 1 468. F H Cl Me OCHF₂ 2 469. F H Br Me OCHF₂ 0 470. F H Br Me OCHF₂ 1 471. F H Br Me OCHF₂ 2 472. F H Br Me CF₃ 0 473. F H Br Me CF₃ 1 474. F H Br Me CF₃ 2 475. F H CF₃ Me CF₃ 0 476. F H CF₃ Me CF₃ 1 477. F H CF₃ Me CF₃ 2 478. F H CHF₂ Me CF₃ 0 479. F H CHF₂ Me CF₃ 1 480. F H CHF₂ Me CF₃ 2 481. F H CF₂CF₃ Me CF₃ 0 482. F H CF₂CF₃ Me CF₃ 1 483. F H CF₂CF₃ Me CF₃ 2 484. F H CF₃ Me CF₂CF₃ 0 485. F H CF₃ Me CF₂CF₃ 1 486. F H CF₃ Me CF₂CF₃ 2 487. F H CHF₂ Me OCH₂CF₃ 0 488. F H CHF₂ Me OCH₂CF₃ 1 489. F H CHF₂ Me OCH₂CF₃ 2 490. F H CHF₂ Me OCHF₂ 0 491. F H CHF₂ Me OCHF₂ 1 492. F H CHF₂ Me OCHF₂ 2 493. Cl H CF₃ Ph Cl 0 494. Cl H CF₃ Ph Cl 1 495. Cl H CF₃ Ph Cl 2 496. Cl H CF₃ tBu Cl 0 497. Cl H CF₃ tBu Cl 1 498. Cl H CF₃ tBu Cl 2 499. Cl H CF₃ CHF₂ Cl 0 500. Cl H CF₃ CHF₂ Cl 1 501. Cl H CF₃ CHF₂ Cl 2 502. Cl H Cl CHF₂ CF₃ 0 503. Cl H Cl CHF₂ CF₃ 1 504. Cl H Cl CHF₂ CF₃ 2 505. Cl H CF₃ Me OMe 0 506. Cl H CF₃ Me OMe 1 507. Cl H CF₃ Me OMe 2 508. Cl H CF₃ Me CN 0 509. Cl H CF₃ Me CN 1 510. Cl H CF₃ Me CN 2 511. Cl H Cl Et Cl 0 512. Cl H Cl Et Cl 1 513. Cl H Cl Et Cl 2 514. Cl H CHF₂ Me Cl 0 515. Cl H CHF₂ Me Cl 1 516. Cl H CHF₂ Me Cl 2 517. Cl H Me Me Me 0 518. Cl H Me Me Me 1 519. Cl H Me Me Me 2 520. Cl H Me Me Cl 0 521. Cl H Me Me Cl 1 522. Cl H Me Me Cl 2 523. Cl H Cl Me Cl 0 524. Cl H Cl Me Cl 1 525. Cl H Cl Me Cl 2 526. Cl H CF₃ Me Cl 0 527. Cl H CF₃ Me Cl 1 528. Cl H CF₃ Me Cl 2 529. Cl H Cl Me CF₃ 0 530. Cl H Cl Me CF₃ 1 531. Cl H Cl Me CF₃ 2 532. Cl H CF₃ Me F 0 533. Cl H CF₃ Me F 1 534. Cl H CF₃ Me F 2 535. Cl H OMe Me CF₃ 0 536. Cl H OMe Me CF₃ 1 537. Cl H OMe Me CF₃ 2 538. Cl H CF₃ Me OEt 0 539. Cl H CF₃ Me OEt 1 540. Cl H CF₃ Me OEt 2 541. Cl H CF₃ Me OCHF₂ 0 542. Cl H CF₃ Me OCHF₂ 1 543. Cl H CF₃ Me OCHF₂ 2 544. Cl H OCHF₂ Me CF₃ 0 545. Cl H OCHF₂ Me CF₃ 1 546. Cl H OCHF₂ Me CF₃ 2 547. Cl H CF₃ Me OCH₂CHF₂ 0 548. Cl H CF₃ Me OCH₂CHF₂ 1 549. Cl H CF₃ Me OCH₂CHF₂ 2 550. Cl H CF₃ Me OCH₂CF₃ 0 551. Cl H CF₃ Me OCH₂CF₃ 1 552. Cl H CF₃ Me OCH₂CF₃ 2 553. Cl H CF₃ Me OCH₂CN 0 554. Cl H CF₃ Me OCH₂CN 1 555. Cl H CF₃ Me OCH₂CN 2 556. Cl H CF₃ Me SO₂Me 0 557. Cl H CF₃ Me SO₂Me 1 558. Cl H CF₃ Me SO₂Me 2 559. Cl H CF₃ Me SEt 0 560. Cl H CF₃ Me SEt 1 561. Cl H CF₃ Me SEt 2 562. Cl H CF₃ Me Me 0 563. Cl H CF₃ Me Me 1 564. Cl H CF₃ Me Me 2 565. Cl H CF₃ Me Et 0 566. Cl H CF₃ Me Et 1 567. Cl H CF₃ Me Et 2 568. Cl H CF₃ Et Cl 0 569. Cl H CF₃ Et Cl 1 570. Cl H CF₃ Et Cl 2 571. Cl H Cl Et CF₃ 0 572. Cl H Cl Et CF₃ 1 573. Cl H Cl Et CF₃ 2 574. Cl H CF₃ iPr Cl 0 575. Cl H CF₃ iPr Cl 1 576. Cl H CF₃ iPr Cl 2 577. Cl H Cl iPr CF₃ 0 578. Cl H Cl iPr CF₃ 1 579. Cl H Cl iPr CF₃ 2 580. Cl H CF₃ tBu Cl 0 581. Cl H CF₃ tBu Cl 1 582. Cl H CF₃ tBu Cl 2 583. Cl H Cl tBu CF₃ 0 584. Cl H Cl tBu CF₃ 1 585. Cl H Cl tBu CF₃ 2 586. Cl H CF₃ cPen Cl 0 587. Cl H CF₃ cPen Cl 1 588. Cl H CF₃ cPen Cl 2 589. Cl H Cl cPen CF₃ 0 590. Cl H Cl cPen CF₃ 1 591. Cl H Cl cPen CF₃ 2 592. Cl H CF₃ CH₂cPr Cl 0 593. Cl H CF₃ CH₂cPr Cl 1 594. Cl H CF₃ CH₂cPr Cl 2 595. Cl H Cl CH₂cPr CF₃ 0 596. Cl H Cl CH₂cPr CF₃ 1 597. Cl H Cl CH₂cPr CF₃ 2 598. Cl H CF₃ CH₂CH═CH₂ Cl 0 599. Cl H CF₃ CH₂CH═CH₂ Cl 1 600. Cl H CF₃ CH₂CH═CH₂ Cl 2 601. Cl H Cl CH₂CH═CH₂ CF₃ 0 602. Cl H Cl CH₂CH═CH₂ CF₃ 1 603. Cl H Cl CH₂CH═CH₂ CF₃ 2 604. Cl H CF₃ CHF₂ OMe 0 605. Cl H CF₃ CHF₂ OMe 1 606. Cl H CF₃ CHF₂ OMe 2 607. Cl H OMe CHF₂ CF₃ 0 608. Cl H OMe CHF₂ CF₃ 1 609. Cl H OMe CHF₂ CF₃ 2 610. Cl H CF₃ CH₂CF₃ Cl 0 611. Cl H CF₃ CH₂CF₃ Cl 1 612. Cl H CF₃ CH₂CF₃ Cl 2 613. Cl H Cl CH₂CF₃ CF₃ 0 614. Cl H Cl CH₂CF₃ CF₃ 1 615. Cl H Cl CH₂CF₃ CF₃ 2 616. Cl H CF₃ CH₂OMe Cl 0 617. Cl H CF₃ CH₂OMe Cl 1 618. Cl H CF₃ CH₂OMe Cl 2 619. Cl H Cl CH₂OMe CF₃ 0 620. Cl H Cl CH₂OMe CF₃ 1 621. Cl H Cl CH₂OMe CF₃ 2 622. Cl H CF₃ CH₂CN Cl 0 623. Cl H CF₃ CH₂CN Cl 1 624. Cl H CF₃ CH₂CN Cl 2 625. Cl H Me Ph Me 0 626. Cl H Me Ph Me 1 627. Cl H Me Ph Me 2 628. Cl H Me Ph Cl 0 629. Cl H Me Ph Cl 1 630. Cl H Me Ph Cl 2 631. Cl H Et Ph Cl 0 632. Cl H Et Ph Cl 1 633. Cl H Et Ph Cl 2 634. Cl H Pr Ph Cl 0 635. Cl H Pr Ph Cl 1 636. Cl H Pr Ph Cl 2 637. Cl H iPr Ph Cl 0 638. Cl H iPr Ph Cl 1 639. Cl H iPr Ph Cl 2 640. Cl H CF₃ Ph Cl 0 641. Cl H CF₃ Ph Cl 1 642. Cl H CF₃ Ph Cl 2 643. Cl H CF₃ Ph Me 0 644. Cl H CF₃ Ph Me 1 645. Cl H CF₃ Ph Me 2 646. Cl H CF₃ Ph CF₃ 0 647. Cl H CF₃ Ph CF₃ 1 648. Cl H CF₃ Ph CF₃ 2 649. Cl H CF₃ Ph F 0 650. Cl H CF₃ Ph F 1 651. Cl H CF₃ Ph F 2 652. Cl H CF₃ Ph OMe 0 653. Cl H CF₃ Ph OMe 1 654. Cl H CF₃ Ph OMe 2 655. Cl H CF₃ Ph OEt 0 656. Cl H CF₃ Ph OEt 1 657. Cl H CF₃ Ph OEt 2 658. Cl H CF₃ Ph OCH F₂ 0 659. Cl H CF₃ Ph OCHF₂ 1 660. Cl H CF₃ Ph OCHF₂ 2 661. Cl H CF₃ Ph CN 0 662. Cl H CF₃ Ph CN 1 663. Cl H CF₃ Ph CN 2 664. Cl H CF₃ Ph(4-Cl) Cl 0 665. Cl H CF₃ Ph(4-Cl) Cl 1 666. Cl H CF₃ Ph(4-Cl) Cl 2 667. Cl H Me Me OCH₂CF₃ 0 668. Cl H Me Me OCH₂CF₃ 1 669. Cl H Me Me OCH₂CF₃ 2 670. Cl H CF₃ Me

0 671. Cl H CF₃ Me

1 672. Cl H CF₃ Me

2 673. Cl H CF₃ Me H 0 674. Cl H CF₃ Me H 1 675. Cl H CF₃ Me H 2 676. Cl H CF₃ Me OCH₂CH₂OMe 0 677. Cl H CF₃ Me OCH₂CH₂OMe 1 678. Cl H CF₃ Me OCH₂CH₂OMe 2 679. Cl H CF₃ Me SMe 0 680. Cl H CF₃ Me SMe 1 681. Cl H CF₃ Me SMe 2 682. Cl H CF₃ Me OCH₂CH₂CH₂F 0 683. Cl H CF₃ Me OCH₂CH₂CH₂F 1 684. Cl H CF₃ Me OCH₂CH₂CH₂F 2 685. Cl H CF₃ Me OCH(CH₂F)₂ 0 686. Cl H CF₃ Me OCH(CH₂F)₂ 1 687. Cl H CF₃ Me OCH(CH₂F)₂ 2 688. Cl H CF₃ Me OCH₂CF₂CHF₂ 0 689. Cl H CF₃ Me OCH₂CF₂CHF₂ 1 690. Cl H CF₃ Me OCH₂CF₂CHF₂ 2 691. Cl H CF₃ Me OCH₂CF═CH₂ 0 692. Cl H CF₃ Me OCH₂CF═CH₂ 1 693. Cl H CF₃ Me OCH₂CF═CH₂ 2 694. Cl H CF₃ Me OCH(Me)CF₃ 0 695. Cl H CF₃ Me OCH(Me)CF₃ 1 696. Cl H CF₃ Me OCH(Me)CF₃ 2 697. Cl H CF₃ Me OCH(Me)CH₂F 0 698. Cl H CF₃ Me OCH(Me)CH₂F 1 699. Cl H CF₃ Me OCH(Me)CH₂F 2 700. Cl H OCH₂CF₃ Me CF₃ 0 701. Cl H OCH₂CF₃ Me CF₃ 1 702. Cl H OCH₂CF₃ Me CF₃ 2 703. Cl H OCH₂CF₃ Me CHF₂ 0 704. Cl H OCH₂CF₃ Me CHF₂ 1 705. Cl H OCH₂CF₃ Me CHF₂ 2 706. Cl H CHF₂ Me CHF₂ 0 707. Cl H CHF₂ Me CHF₂ 1 708. Cl H CHF₂ Me CHF₂ 2 709. Cl H CF₃ Me CHF₂ 0 710. Cl H CF₃ Me CHF₂ 1 711. Cl H CF₃ Me CHF₂ 2 712. Cl H Cl Me OCHF₂ 0 713. Cl H Cl Me OCHF₂ 1 714. Cl H Cl Me OCHF₂ 2 715. Cl H Br Me OCHF₂ 0 716. Cl H Br Me OCHF₂ 1 717. Cl H Br Me OCHF₂ 2 718. Cl H Br Me CF₃ 0 719. Cl H Br Me CF₃ 1 720. Cl H Br Me CF₃ 2 721. Cl H CF₃ Me CF₃ 0 722. Cl H CF₃ Me CF₃ 1 723. Cl H CF₃ Me CF₃ 2 724. Cl H CHF₂ Me CF₃ 0 725. Cl H CHF₂ Me CF₃ 1 726. Cl H CHF₂ Me CF₃ 2 727. Cl H CF₂CF₃ Me CF₃ 0 728. Cl H CF₂CF₃ Me CF₃ 1 729. Cl H CF₂CF₃ Me CF₃ 2 730. Cl H CF₃ Me CF₂CF₃ 0 731. Cl H CF₃ Me CF₂CF₃ 1 732. Cl H CF₃ Me CF₂CF₃ 2 733. Cl H CHF₂ Me OCH₂CF₃ 0 734. Cl H CHF₂ Me OCH₂CF₃ 1 735. Cl H CHF₂ Me OCH₂CF₃ 2 736. Cl H CHF₂ Me OCHF₂ 0 737. Cl H CHF₂ Me OCHF₂ 1 738. Cl H CHF₂ Me OCHF₂ 2 739. Br H CF₃ Ph Cl 0 740. Br H CF₃ Ph Cl 1 741. Br H CF₃ Ph Cl 2 742. Br H CF₃ tBu Cl 0 743. Br H CF₃ tBu Cl 1 744. Br H CF₃ tBu Cl 2 745. Br H CF₃ CHF₂ Cl 0 746. Br H CF₃ CHF₂ Cl 1 747. Br H CF₃ CHF₂ Cl 2 748. Br H Cl CHF₂ CF₃ 0 749. Br H Cl CHF₂ CF₃ 1 750. Br H Cl CHF₂ CF₃ 2 751. Br H CF₃ Me OMe 0 752. Br H CF₃ Me OMe 1 753. Br H CF₃ Me OMe 2 754. Br H CF₃ Me CN 0 755. Br H CF₃ Me CN 1 756. Br H CF₃ Me CN 2 757. Br H Cl Et Cl 0 758. Br H Cl Et Cl 1 759. Br H Cl Et Cl 2 760. Br H CHF₂ Me Cl 0 761. Br H CHF₂ Me Cl 1 762. Br H CHF₂ Me Cl 2 763. Br H Me Me Me 0 764. Br H Me Me Me 1 765. Br H Me Me Me 2 766. Br H Me Me Cl 0 767. Br H Me Me Cl 1 768. Br H Me Me Cl 2 769. Br H Cl Me Cl 0 770. Br H Cl Me Cl 1 771. Br H Cl Me Cl 2 772. Br H CF₃ Me Cl 0 773. Br H CF₃ Me Cl 1 774. Br H CF₃ Me Cl 2 775. Br H Cl Me CF₃ 0 776. Br H Cl Me CF₃ 1 777. Br H Cl Me CF₃ 2 778. Br H CF₃ Me F 0 779. Br H CF₃ Me F 1 780. Br H CF₃ Me F 2 781. Br H OMe Me CF₃ 0 782. Br H OMe Me CF₃ 1 783. Br H OMe Me CF₃ 2 784. Br H CF₃ Me OEt 0 785. Br H CF₃ Me OEt 1 786. Br H CF₃ Me OEt 2 787. Br H CF₃ Me OCHF₂ 0 788. Br H CF₃ Me OCHF₂ 1 789. Br H CF₃ Me OCHF₂ 2 790. Br H OCHF₂ Me CF₃ 0 791. Br H OCHF₂ Me CF₃ 1 792. Br H OCHF₂ Me CF₃ 2 793. Br H CF₃ Me OCH₂CHF₂ 0 794. Br H CF₃ Me OCH₂CHF₂ 1 795. Br H CF₃ Me OCH₂CHF₂ 2 796. Br H CF₃ Me OCH₂CF₃ 0 797. Br H CF₃ Me OCH₂CF₃ 1 798. Br H CF₃ Me OCH₂CF₃ 2 799. Br H CF₃ Me OCH₂CN 0 800. Br H CF₃ Me OCH₂CN 1 801. Br H CF₃ Me OCH₂CN 2 802. Br H CF₃ Me SO₂Me 0 803. Br H CF₃ Me SO₂Me 1 804. Br H CF₃ Me SO₂Me 2 805. Br H CF₃ Me SEt 0 806. Br H CF₃ Me SEt 1 807. Br H CF₃ Me SEt 2 808. Br H CF₃ Me Me 0 809. Br H CF₃ Me Me 1 810. Br H CF₃ Me Me 2 811. Br H CF₃ Me Et 0 812. Br H CF₃ Me Et 1 813. Br H CF₃ Me Et 2 814. Br H CF₃ Et Cl 0 815. Br H CF₃ Et Cl 1 816. Br H CF₃ Et Cl 2 817. Br H Cl Et CF₃ 0 818. Br H Cl Et CF₃ 1 819. Br H Cl Et CF₃ 2 820. Br H CF₃ iPr Cl 0 821. Br H CF₃ iPr Cl 1 822. Br H CF₃ iPr Cl 2 823. Br H Cl iPr CF₃ 0 824. Br H Cl iPr CF₃ 1 825. Br H Cl iPr CF₃ 2 826. Br H CF₃ tBu Cl 0 827. Br H CF₃ tBu Cl 1 828. Br H CF₃ tBu Cl 2 829. Br H Cl tBu CF₃ 0 830. Br H Cl tBu CF₃ 1 831. Br H Cl tBu CF₃ 2 832. Br H CF₃ cPen Cl 0 833. Br H CF₃ cPen Cl 1 834. Br H CF₃ cPen Cl 2 835. Br H Cl cPen CF₃ 0 836. Br H Cl cPen CF₃ 1 837. Br H Cl cPen CF₃ 2 838. Br H CF₃ CH₂cPr Cl 0 839. Br H CF₃ CH₂cPr Cl 1 840. Br H CF₃ CH₂cPr Cl 2 841. Br H Cl CH₂cPr CF₃ 0 842. Br H Cl CH₂cPr CF₃ 1 843. Br H Cl CH₂cPr CF₃ 2 844. Br H CF₃ CH₂CH═CH₂ Cl 0 845. Br H CF₃ CH₂CH═CH₂ Cl 1 846. Br H CF₃ CH₂CH═CH₂ Cl 2 847. Br H Cl CH₂CH═CH₂ CF₃ 0 848. Br H Cl CH₂CH═CH₂ CF₃ 1 849. Br H Cl CH₂CH═CH₂ CF₃ 2 850. Br H CF₃ CHF₂ OMe 0 851. Br H CF₃ CHF₂ OMe 1 852. Br H CF₃ CHF₂ OMe 2 853. Br H OMe CHF₂ CF₃ 0 854. Br H OMe CHF₂ CF₃ 1 855. Br H OMe CHF₂ CF₃ 2 856. Br H CF₃ CH₂CF₃ Cl 0 857. Br H CF₃ CH₂CF₃ Cl 1 858. Br H CF₃ CH₂CF₃ Cl 2 859. Br H Cl CH₂CF₃ CF₃ 0 860. Br H Cl CH₂CF₃ CF₃ 1 861. Br H Cl CH₂CF₃ CF₃ 2 862. Br H CF₃ CH₂OMe Cl 0 863. Br H CF₃ CH₂OMe Cl 1 864. Br H CF₃ CH₂OMe Cl 2 865. Br H Cl CH₂OMe CF₃ 0 866. Br H Cl CH₂OMe CF₃ 1 867. Br H Cl CH₂OMe CF₃ 2 868. Br H CF₃ CH₂CN Cl 0 869. Br H CF₃ CH₂CN Cl 1 870. Br H CF₃ CH₂CN Cl 2 871. Br H Me Ph Me 0 872. Br H Me Ph Me 1 873. Br H Me Ph Me 2 874. Br H Me Ph Cl 0 875. Br H Me Ph Cl 1 876. Br H Me Ph Cl 2 877. Br H Et Ph Cl 0 878. Br H Et Ph Cl 1 879. Br H Et Ph Cl 2 880. Br H Pr Ph Cl 0 881. Br H Pr Ph Cl 1 882. Br H Pr Ph Cl 2 883. Br H iPr Ph Cl 0 884. Br H iPr Ph Cl 1 885. Br H iPr Ph Cl 2 886. Br H CF₃ Ph Cl 0 887. Br H CF₃ Ph Cl 1 888. Br H CF₃ Ph Cl 2 889. Br H CF₃ Ph Me 0 890. Br H CF₃ Ph Me 1 891. Br H CF₃ Ph Me 2 892. Br H CF₃ Ph CF₃ 0 893. Br H CF₃ Ph CF₃ 1 894. Br H CF₃ Ph CF₃ 2 895. Br H CF₃ Ph F 0 896. Br H CF₃ Ph F 1 897. Br H CF₃ Ph F 2 898. Br H CF₃ Ph OMe 0 899. Br H CF₃ Ph OMe 1 900. Br H CF₃ Ph OMe 2 901. Br H CF₃ Ph OEt 0 902. Br H CF₃ Ph OEt 1 903. Br H CF₃ Ph OEt 2 904. Br H CF₃ Ph OCHF₂ 0 905. Br H CF₃ Ph OCHF₂ 1 906. Br H CF₃ Ph OCHF₂ 2 907. Br H CF₃ Ph CN 0 908. Br H CF₃ Ph CN 1 909. Br H CF₃ Ph CN 2 910. Br H CF₃ Ph(4-Cl) Cl 0 911. Br H CF₃ Ph(4-Cl) Cl 1 912. Br H CF₃ Ph(4-Cl) Cl 2 913. Br H Me Me OCH₂CF₃ 0 914. Br H Me Me OCH₂CF₃ 1 915. Br H Me Me OCH₂CF₃ 2 916. Br H CF₃ Me

0 917. Br H CF₃ Me

1 918. Br H CF₃ Me

2 919. Br H CF₃ Me H 0 920. Br H CF₃ Me H 1 921. Br H CF₃ Me H 2 922. Br H CF₃ Me OCH₂CH₂OMe 0 923. Br H CF₃ Me OCH₂CH₂OMe 1 924. Br H CF₃ Me OCH₂CH₂OMe 2 925. Br H CF₃ Me SMe 0 926. Br H CF₃ Me SMe 1 927. Br H CF₃ Me SMe 2 928. Br H CF₃ Me OCH₂CH₂CH₂F 0 929. Br H CF₃ Me OCH₂CH₂CH₂F 1 930. Br H CF₃ Me OCH₂CH₂CH₂F 2 931. Br H CF₃ Me OCH(CH₂F)₂ 0 932. Br H CF₃ Me OCH(CH₂F)₂ 1 933. Br H CF₃ Me OCH(CH₂F)₂ 2 934. Br H CF₃ Me OCH₂CF₂CHF₂ 0 935. Br H CF₃ Me OCH₂CF₂CHF₂ 1 936. Br H CF₃ Me OCH₂CF₂CHF₂ 2 937. Br H CF₃ Me OCH₂CF═CH₂ 0 938. Br H CF₃ Me OCH₂CF═CH₂ 1 939. Br H CF₃ Me OCH₂CF═CH₂ 2 940. Br H CF₃ Me OCH(Me)CF₃ 0 941. Br H CF₃ Me OCH(Me)CF₃ 1 942. Br H CF₃ Me OCH(Me)CF₃ 2 943. Br H CF₃ Me OCH(Me)CH₂F 0 944. Br H CF₃ Me OCH(Me)CH₂F 1 945. Br H CF₃ Me OCH(Me)CH₂F 2 946. Br H OCH₂CF₃ Me CF₃ 0 947. Br H OCH₂CF₃ Me CF₃ 1 948. Br H OCH₂CF₃ Me CF₃ 2 949. Br H OCH₂CF₃ Me CHF₂ 0 950. Br H OCH₂CF₃ Me CHF₂ 1 951. Br H OCH₂CF₃ Me CHF₂ 2 952. Br H CHF₂ Me CHF₂ 0 953. Br H CHF₂ Me CHF₂ 1 954. Br H CHF₂ Me CHF₂ 2 955. Br H CF₃ Me CHF₂ 0 956. Br H CF₃ Me CHF₂ 1 957. Br H CF₃ Me CHF₂ 2 958. Br H Cl Me OCHF₂ 0 959. Br H Cl Me OCHF₂ 1 960. Br H Cl Me OCHF₂ 2 961. Br H Br Me OCHF₂ 0 962. Br H Br Me OCHF₂ 1 963. Br H Br Me OCHF₂ 2 964. Br H Br Me CF₃ 0 965. Br H Br Me CF₃ 1 966. Br H Br Me CF₃ 2 967. Br H CF₃ Me CF₃ 0 968. Br H CF₃ Me CF₃ 1 969. Br H CF₃ Me CF₃ 2 970. Br H CHF₂ Me CF₃ 0 971. Br H CHF₂ Me CF₃ 1 972. Br H CHF₂ Me CF₃ 2 973. Br H CF₂CF₃ Me CF₃ 0 974. Br H CF₂CF₃ Me CF₃ 1 975. Br H CF₂CF₃ Me CF₃ 2 976. Br H CF₃ Me CF₂CF₃ 0 977. Br H CF₃ Me CF₂CF₃ 1 978. Br H CF₃ Me CF₂CF₃ 2 979. Br H CHF₂ Me OCH₂CF₃ 0 980. Br H CHF₂ Me OCH₂CF₃ 1 981. Br H CHF₂ Me OCH₂CF₃ 2 982. Br H CHF₂ Me OCHF₂ 0 983. Br H CHF₂ Me OCHF₂ 1 984. Br H CHF₂ Me OCHF₂ 2 985. I H CF₃ Ph Cl 0 986. I H CF₃ Ph Cl 1 987. I H CF₃ Ph Cl 2 988. I H CF₃ tBu Cl 0 989. I H CF₃ tBu Cl 1 990. I H CF₃ tBu Cl 2 991. I H CF₃ CHF₂ Cl 0 992. I H CF₃ CHF₂ Cl 1 993. I H CF₃ CHF₂ Cl 2 994. I H Cl CHF₂ CF₃ 0 995. I H Cl CHF₂ CF₃ 1 996. I H Cl CHF₂ CF₃ 2 997. I H CF₃ Me OMe 0 998. I H CF₃ Me OMe 1 999. I H CF₃ Me OMe 2 1000. I H CF₃ Me CN 0 1001. I H CF₃ Me CN 1 1002. I H CF₃ Me CN 2 1003. I H Cl Et Cl 0 1004. I H Cl Et Cl 1 1005. I H Cl Et Cl 2 1006. I H CHF₂ Me Cl 0 1007. I H CHF₂ Me Cl 1 1008. I H CHF₂ Me Cl 2 1009. I H Me Me Me 0 1010. I H Me Me Me 1 1011. I H Me Me Me 2 1012. I H Me Me Cl 0 1013. I H Me Me Cl 1 1014. I H Me Me Cl 2 1015. I H Cl Me Cl 0 1016. I H Cl Me Cl 1 1017. I H Cl Me Cl 2 1018. I H CF₃ Me Cl 0 1019. I H CF₃ Me Cl 1 1020. I H CF₃ Me Cl 2 1021. I H Cl Me CF₃ 0 1022. I H Cl Me CF₃ 1 1023. I H Cl Me CF₃ 2 1024. I H CF₃ Me F 0 1025. I H CF₃ Me F 1 1026. I H CF₃ Me F 2 1027. I H OMe Me CF₃ 0 1028. I H OMe Me CF₃ 1 1029. I H OMe Me CF₃ 2 1030. I H CF₃ Me OEt 0 1031. I H CF₃ Me OEt 1 1032. I H CF₃ Me OEt 2 1033. I H CF₃ Me OCHF₂ 0 1034. I H CF₃ Me OCHF₂ 1 1035. I H CF₃ Me OCHF₂ 2 1036. I H OCHF₂ Me CF₃ 0 1037. I H OCHF₂ Me CF₃ 1 1038. I H OCHF₂ Me CF₃ 2 1039. I H CF₃ Me OCH₂CHF₂ 0 1040. I H CF₃ Me OCH₂CHF₂ 1 1041. I H CF₃ Me OCH₂CHF₂ 2 1042. I H CF₃ Me OCH₂CF₃ 0 1043. I H CF₃ Me OCH₂CF₃ 1 1044. I H CF₃ Me OCH₂CF₃ 2 1045. I H CF₃ Me OCH₂CN 0 1046. I H CF₃ Me OCH₂CN 1 1047. I H CF₃ Me OCH₂CN 2 1048. I H CF₃ Me SO₂Me 0 1049. I H CF₃ Me SO₂Me 1 1050. I H CF₃ Me SO₂Me 2 1051. I H CF₃ Me SEt 0 1052. I H CF₃ Me SEt 1 1053. I H CF₃ Me SEt 2 1054. I H CF₃ Me Me 0 1055. I H CF₃ Me Me 1 1056. I H CF₃ Me Me 2 1057. I H CF₃ Me Et 0 1058. I H CF₃ Me Et 1 1059. I H CF₃ Me Et 2 1060. I H CF₃ Et Cl 0 1061. I H CF₃ Et Cl 1 1062. I H CF₃ Et Cl 2 1063. I H Cl Et CF₃ 0 1064. I H Cl Et CF₃ 1 1065. I H Cl Et CF₃ 2 1066. I H CF₃ iPr Cl 0 1067. I H CF₃ iPr Cl 1 1068. I H CF₃ iPr Cl 2 1069. I H Cl iPr CF₃ 0 1070. I H Cl iPr CF₃ 1 1071. I H Cl iPr CF₃ 2 1072. I H CF₃ tBu Cl 0 1073. I H CF₃ tBu Cl 1 1074. I H CF₃ tBu Cl 2 1075. I H Cl tBu CF₃ 0 1076. I H Cl tBu CF₃ 1 1077. I H Cl tBu CF₃ 2 1078. I H CF₃ cPen Cl 0 1079. I H CF₃ cPen Cl 1 1080. I H CF₃ cPen Cl 2 1081. I H Cl cPen CF₃ 0 1082. I H Cl cPen CF₃ 1 1083. I H Cl cPen CF₃ 2 1084. I H CF₃ CH₂cPr Cl 0 1085. I H CF₃ CH₂cPr Cl 1 1086. I H CF₃ CH₂cPr Cl 2 1087. I H Cl CH₂cPr CF₃ 0 1088. I H Cl CH₂cPr CF₃ 1 1089. I H Cl CH₂cPr CF₃ 2 1090. I H CF₃ CH₂CH═CH₂ Cl 0 1091. I H CF₃ CH₂CH═CH₂ Cl 1 1092. I H CF₃ CH₂CH═CH₂ Cl 2 1093. I H Cl CH₂CH═CH₂ CF₃ 0 1094. I H Cl CH₂CH═CH₂ CF₃ 1 1095. I H Cl CH₂CH═CH₂ CF₃ 2 1096. I H CF₃ CHF₂ OMe 0 1097. I H CF₃ CHF₂ OMe 1 1098. I H CF₃ CHF₂ OMe 2 1099. I H OMe CHF₂ CF₃ 0 1100. I H OMe CHF₂ CF₃ 1 1101. I H OMe CHF₂ CF₃ 2 1102. I H CF₃ CH₂CF₃ Cl 0 1103. I H CF₃ CH₂CF₃ Cl 1 1104. I H CF₃ CH₂CF₃ Cl 2 1105. I H Cl CH₂CF₃ CF₃ 0 1106. I H Cl CH₂CF₃ CF₃ 1 1107. I H Cl CH₂CF₃ CF₃ 2 1108. I H CF₃ CH₂OMe Cl 0 1109. I H CF₃ CH₂OMe Cl 1 1110. I H CF₃ CH₂OMe Cl 2 1111. I H Cl CH₂OMe CF₃ 0 1112. I H Cl CH₂OMe CF₃ 1 1113. I H Cl CH₂OMe CF₃ 2 1114. I H CF₃ CH₂CN Cl 0 1115. I H CF₃ CH₂CN Cl 1 1116. I H CF₃ CH₂CN Cl 2 1117. I H Me Ph Me 0 1118. I H Me Ph Me 1 1119. I H Me Ph Me 2 1120. I H Me Ph Cl 0 1121. I H Me Ph Cl 1 1122. I H Me Ph Cl 2 1123. I H Et Ph Cl 0 1124. I H Et Ph Cl 1 1125. I H Et Ph Cl 2 1126. I H Pr Ph Cl 0 1127. I H Pr Ph Cl 1 1128. I H Pr Ph Cl 2 1129. I H iPr Ph Cl 0 1130. I H iPr Ph Cl 1 1131. I H iPr Ph Cl 2 1132. I H CF₃ Ph Cl 0 1133. I H CF₃ Ph Cl 1 1134. I H CF₃ Ph Cl 2 1135. I H CF₃ Ph Me 0 1136. I H CF₃ Ph Me 1 1137. I H CF₃ Ph Me 2 1138. I H CF₃ Ph CF₃ 0 1139. I H CF₃ Ph CF₃ 1 1140. I H CF₃ Ph CF₃ 2 1141. I H CF₃ Ph F 0 1142. I H CF₃ Ph F 1 1143. I H CF₃ Ph F 2 1144. I H CF₃ Ph OMe 0 1145. I H CF₃ Ph OMe 1 1146. I H CF₃ Ph OMe 2 1147. I H CF₃ Ph OEt 0 1148. I H CF₃ Ph OEt 1 1149. I H CF₃ Ph OEt 2 1150. I H CF₃ Ph OCHF₂ 0 1151. I H CF₃ Ph OCHF₂ 1 1152. I H CF₃ Ph OCHF₂ 2 1153. I H CF₃ Ph CN 0 1154. I H CF₃ Ph CN 1 1155. I H CF₃ Ph CN 2 1156. I H CF₃ Ph(4-Cl) Cl 0 1157. I H CF₃ Ph(4-Cl) Cl 1 1158. I H CF₃ Ph(4-Cl) Cl 2 1159. I H Me Me OCH₂CF₃ 0 1160. I H Me Me OCH₂CF₃ 1 1161. I H Me Me OCH₂CF₃ 2 1162. I H CF₃ Me

0 1163. I H CF₃ Me

1 1164. I H CF₃ Me

2 1165. I H CF₃ Me H 0 1166. I H CF₃ Me H 1 1167. I H CF₃ Me H 2 1168. I H CF₃ Me OCH₂CH₂OMe 0 1169. I H CF₃ Me OCH₂CH₂OMe 1 1170. I H CF₃ Me OCH₂CH₂OMe 2 1171. I H CF₃ Me SMe 0 1172. I H CF₃ Me SMe 1 1173. I H CF₃ Me SMe 2 1174. I H CF₃ Me OCH₂CH₂CH₂F 0 1175. I H CF₃ Me OCH₂CH₂CH₂F 1 1176. I H CF₃ Me OCH₂CH₂CH₂F 2 1177. I H CF₃ Me OCH(CH₂F)₂ 0 1178. I H CF₃ Me OCH(CH₂F)₂ 1 1179. I H CF₃ Me OCH(CH₂F)₂ 2 1180. I H CF₃ Me OCH₂CF₂CHF₂ 0 1181. I H CF₃ Me OCH₂CF₂CHF₂ 1 1182. I H CF₃ Me OCH₂CF₂CHF₂ 2 1183. I H CF₃ Me OCH₂CF═CH₂ 0 1184. I H CF₃ Me OCH₂CF═CH₂ 1 1185. I H CF₃ Me OCH₂CF═CH₂ 2 1186. I H CF₃ Me OCH(Me)CF₃ 0 1187. I H CF₃ Me OCH(Me)CF₃ 1 1188. I H CF₃ Me OCH(Me)CF₃ 2 1189. I H CF₃ Me OCH(Me)CH₂F 0 1190. I H CF₃ Me OCH(Me)CH₂F 1 1191. I H CF₃ Me OCH(Me)CH₂F 2 1192. I H OCH₂CF₃ Me CF₃ 0 1193. I H OCH₂CF₃ Me CF₃ 1 1194. I H OCH₂CF₃ Me CF₃ 2 1195. I H OCH₂CF₃ Me CHF₂ 0 1196. I H OCH₂CF₃ Me CHF₂ 1 1197. I H OCH₂CF₃ Me CHF₂ 2 1198. I H CHF₂ Me CHF₂ 0 1199. I H CHF₂ Me CHF₂ 1 1200. I H CHF₂ Me CHF₂ 2 1201. I H CF₃ Me CHF₂ 0 1202. I H CF₃ Me CHF₂ 1 1203. I H CF₃ Me CHF₂ 2 1204. I H Cl Me OCHF₂ 0 1205. I H Cl Me OCHF₂ 1 1206. I H Cl Me OCHF₂ 2 1207. I H Br Me OCHF₂ 0 1208. I H Br Me OCHF₂ 1 1209. I H Br Me OCHF₂ 2 1210. I H Br Me CF₃ 0 1211. I H Br Me CF₃ 1 1212. I H Br Me CF₃ 2 1213. I H CF₃ Me CF₃ 0 1214. I H CF₃ Me CF₃ 1 1215. I H CF₃ Me CF₃ 2 1216. I H CHF₂ Me CF₃ 0 1217. I H CHF₂ Me CF₃ 1 1218. I H CHF₂ Me CF₃ 2 1219. I H CF₂CF₃ Me CF₃ 0 1220. I H CF₂CF₃ Me CF₃ 1 1221. I H CF₂CF₃ Me CF₃ 2 1222. I H CF₃ Me CF₂CF₃ 0 1223. I H CF₃ Me CF₂CF₃ 1 1224. I H CF₃ Me CF₂CF₃ 2 1225. I H CHF₂ Me OCH₂CF₃ 0 1226. I H CHF₂ Me OCH₂CF₃ 1 1227. I H CHF₂ Me OCH₂CF₃ 2 1228. I H CHF₂ Me OCHF₂ 0 1229. I H CHF₂ Me OCHF₂ 1 1230. I H CHF₂ Me OCHF₂ 2 1231. H F CF₃ Ph Cl 0 1232. H F CF₃ Ph Cl 1 1233. H F CF₃ Ph Cl 2 1234. H F CF₃ tBu Cl 0 1235. H F CF₃ tBu Cl 1 1236. H F CF₃ tBu Cl 2 1237. H F CF₃ CHF₂ Cl 0 1238. H F CF₃ CHF₂ Cl 1 1239. H F CF₃ CHF₂ Cl 2 1240. H F Cl CHF₂ CF₃ 0 1241. H F Cl CHF₂ CF₃ 1 1242. H F Cl CHF₂ CF₃ 2 1243. H F CF₃ Me OMe 0 1244. H F CF₃ Me OMe 1 1245. H F CF₃ Me OMe 2 1246. H F CF₃ Me CN 0 1247. H F CF₃ Me CN 1 1248. H F CF₃ Me CN 2 1249. H F Cl Et Cl 0 1250. H F Cl Et Cl 1 1251. H F Cl Et Cl 2 1252. H F CHF₂ Me Cl 0 1253. H F CHF₂ Me Cl 1 1254. H F CHF₂ Me Cl 2 1255. H F Me Me Me 0 1256. H F Me Me Me 1 1257. H F Me Me Me 2 1258. H F Me Me Cl 0 1259. H F Me Me Cl 1 1260. H F Me Me Cl 2 1261. H F Cl Me Cl 0 1262. H F Cl Me Cl 1 1263. H F Cl Me Cl 2 1264. H F CF₃ Me Cl 0 1265. H F CF₃ Me Cl 1 1266. H F CF₃ Me Cl 2 1267. H F Cl Me CF₃ 0 1268. H F Cl Me CF₃ 1 1269. H F Cl Me CF₃ 2 1270. H F CF₃ Me F 0 1271. H F CF₃ Me F 1 1272. H F CF₃ Me F 2 1273. H F OMe Me CF₃ 0 1274. H F OMe Me CF₃ 1 1275. H F OMe Me CF₃ 2 1276. H F CF₃ Me OEt 0 1277. H F CF₃ Me OEt 1 1278. H F CF₃ Me OEt 2 1279. H F CF₃ Me OCHF₂ 0 1280. H F CF₃ Me OCHF₂ 1 1281. H F CF₃ Me OCHF₂ 2 1282. H F OCHF₂ Me CF₃ 0 1283. H F OCHF₂ Me CF₃ 1 1284. H F OCHF₂ Me CF₃ 2 1285. H F CF₃ Me OCH₂CHF₂ 0 1286. H F CF₃ Me OCH₂CHF₂ 1 1287. H F CF₃ Me OCH₂CHF₂ 2 1288. H F CF₃ Me OCH₂CF₃ 0 1289. H F CF₃ Me OCH₂CF₃ 1 1290. H F CF₃ Me OCH₂CF₃ 2 1291. H F CF₃ Me OCH₂CN 0 1292. H F CF₃ Me OCH₂CN 1 1293. H F CF₃ Me OCH₂CN 2 1294. H F CF₃ Me SO₂Me 0 1295. H F CF₃ Me SO₂Me 1 1296. H F CF₃ Me SO₂Me 2 1297. H F CF₃ Me SEt 0 1298. H F CF₃ Me SEt 1 1299. H F CF₃ Me SEt 2 1300. H F CF₃ Me Me 0 1301. H F CF₃ Me Me 1 1302. H F CF₃ Me Me 2 1303. H F CF₃ Me Et 0 1304. H F CF₃ Me Et 1 1305. H F CF₃ Me Et 2 1306. H F CF₃ Et Cl 0 1307. H F CF₃ Et Cl 1 1308. H F CF₃ Et Cl 2 1309. H F Cl Et CF₃ 0 1310. H F Cl Et CF₃ 1 1311. H F Cl Et CF₃ 2 1312. H F CF₃ iPr Cl 0 1313. H F CF₃ iPr Cl 1 1314. H F CF₃ iPr Cl 2 1315. H F Cl iPr CF₃ 0 1316. H F Cl iPr CF₃ 1 1317. H F Cl iPr CF₃ 2 1318. H F CF₃ tBu Cl 0 1319. H F CF₃ tBu Cl 1 1320. H F CF₃ tBu Cl 2 1321. H F Cl tBu CF₃ 0 1322. H F Cl tBu CF₃ 1 1323. H F Cl tBu CF₃ 2 1324. H F CF₃ cPen Cl 0 1325. H F CF₃ cPen Cl 1 1326. H F CF₃ cPen Cl 2 1327. H F Cl cPen CF₃ 0 1328. H F Cl cPen CF₃ 1 1329. H F Cl cPen CF₃ 2 1330. H F CF₃ CH₂cPr Cl 0 1331. H F CF₃ CH₂cPr Cl 1 1332. H F CF₃ CH₂cPr Cl 2 1333. H F Cl CH₂cPr CF₃ 0 1334. H F Cl CH₂cPr CF₃ 1 1335. H F Cl CH₂cPr CF₃ 2 1336. H F CF₃ CH₂CH═CH₂ Cl 0 1337. H F CF₃ CH₂CH═CH₂ Cl 1 1338. H F CF₃ CH₂CH═CH₂ Cl 2 1339. H F Cl CH₂CH═CH₂ CF₃ 0 1340. H F Cl CH₂CH═CH₂ CF₃ 1 1341. H F Cl CH₂CH═CH₂ CF₃ 2 1342. H F CF₃ CHF₂ OMe 0 1343. H F CF₃ CHF₂ OMe 1 1344. H F CF₃ CHF₂ OMe 2 1345. H F OMe CHF₂ CF₃ 0 1346. H F OMe CHF₂ CF₃ 1 1347. H F OMe CHF₂ CF₃ 2 1348. H F CF₃ CH₂CF₃ Cl 0 1349. H F CF₃ CH₂CF₃ Cl 1 1350. H F CF₃ CH₂CF₃ Cl 2 1351. H F Cl CH₂CF₃ CF₃ 0 1352. H F Cl CH₂CF₃ CF₃ 1 1353. H F Cl CH₂CF₃ CF₃ 2 1354. H F CF₃ CH₂OMe Cl 0 1355. H F CF₃ CH₂OMe Cl 1 1356. H F CF₃ CH₂OMe Cl 2 1357. H F Cl CH₂OMe CF₃ 0 1358. H F Cl CH₂OMe CF₃ 1 1359. H F Cl CH₂OMe CF₃ 2 1360. H F CF₃ CH₂CN Cl 0 1361. H F CF₃ CH₂CN Cl 1 1362. H F CF₃ CH₂CN Cl 2 1363. H F Me Ph Me 0 1364. H F Me Ph Me 1 1365. H F Me Ph Me 2 1366. H F Me Ph Cl 0 1367. H F Me Ph Cl 1 1368. H F Me Ph Cl 2 1369. H F Et Ph Cl 0 1370. H F Et Ph Cl 1 1371. H F Et Ph Cl 2 1372. H F Pr Ph Cl 0 1373. H F Pr Ph Cl 1 1374. H F Pr Ph Cl 2 1375. H F iPr Ph Cl 0 1376. H F iPr Ph Cl 1 1377. H F iPr Ph Cl 2 1378. H F CF₃ Ph Cl 0 1379. H F CF₃ Ph Cl 1 1380. H F CF₃ Ph Cl 2 1381. H F CF₃ Ph Me 0 1382. H F CF₃ Ph Me 1 1383. H F CF₃ Ph Me 2 1384. H F CF₃ Ph CF₃ 0 1385. H F CF₃ Ph CF₃ 1 1386. H F CF₃ Ph CF₃ 2 1387. H F CF₃ Ph F 0 1388. H F CF₃ Ph F 1 1389. H F CF₃ Ph F 2 1390. H F CF₃ Ph OMe 0 1391. H F CF₃ Ph OMe 1 1392. H F CF₃ Ph OMe 2 1393. H F CF₃ Ph OEt 0 1394. H F CF₃ Ph OEt 1 1395. H F CF₃ Ph OEt 2 1396. H F CF₃ Ph OCHF₂ 0 1397. H F CF₃ Ph OCHF₂ 1 1398. H F CF₃ Ph OCHF₂ 2 1399. H F CF₃ Ph CN 0 1400. H F CF₃ Ph CN 1 1401. H F CF₃ Ph CN 2 1402. H F CF₃ Ph(4-Cl) Cl 0 1403. H F CF₃ Ph(4-Cl) Cl 1 1404. H F CF₃ Ph(4-Cl) Cl 2 1405. H F Me Me OCH₂CF₃ 0 1406. H F Me Me OCH₂CF₃ 1 1407. H F Me Me OCH₂CF₃ 2 1408. H F CF₃ Me

0 1409. H F CF₃ Me

1 1410. H F CF₃ Me

2 1411. H F CF₃ Me H 0 1412. H F CF₃ Me H 1 1413. H F CF₃ Me H 2 1414. H F CF₃ Me OCH₂CH₂OMe 0 1415. H F CF₃ Me OCH₂CH₂OMe 1 1416. H F CF₃ Me OCH₂CH₂OMe 2 1417. H F CF₃ Me SMe 0 1418. H F CF₃ Me SMe 1 1419. H F CF₃ Me SMe 2 1420. H F CF₃ Me OCH₂CH₂CH₂F 0 1421. H F CF₃ Me OCH₂CH₂CH₂F 1 1422. H F CF₃ Me OCH₂CH₂CH₂F 2 1423. H F CF₃ Me OCH(CH₂F)₂ 0 1424. H F CF₃ Me OCH(CH₂F)₂ 1 1425. H F CF₃ Me OCH(CH₂F)₂ 2 1426. H F CF₃ Me OCH₂CF₂CHF₂ 0 1427. H F CF₃ Me OCH₂CF₂CHF₂ 1 1428. H F CF₃ Me OCH₂CF₂CHF₂ 2 1429. H F CF₃ Me OCH₂CF═CH₂ 0 1430. H F CF₃ Me OCH₂CF═CH₂ 1 1431. H F CF₃ Me OCH₂CF═CH₂ 2 1432. H F CF₃ Me OCH(Me)CF₃ 0 1433. H F CF₃ Me OCH(Me)CF₃ 1 1434. H F CF₃ Me OCH(Me)CF₃ 2 1435. H F CF₃ Me OCH(Me)CH₂F 0 1436. H F CF₃ Me OCH(Me)CH₂F 1 1437. H F CF₃ Me OCH(Me)CH₂F 2 1438. H F OCH₂CF₃ Me CF₃ 0 1439. H F OCH₂CF₃ Me CF₃ 1 1440. H F OCH₂CF₃ Me CF₃ 2 1441. H F OCH₂CF₃ Me CHF₂ 0 1442. H F OCH₂CF₃ Me CHF₂ 1 1443. H F OCH₂CF₃ Me CHF₂ 2 1444. H F CHF₂ Me CHF₂ 0 1445. H F CHF₂ Me CHF₂ 1 1446. H F CHF₂ Me CHF₂ 2 1447. H F CF₃ Me CHF₂ 0 1448. H F CF₃ Me CHF₂ 1 1449. H F CF₃ Me CHF₂ 2 1450. H F Cl Me OCHF₂ 0 1451. H F Cl Me OCHF₂ 1 1452. H F Cl Me OCHF₂ 2 1453. H F Br Me OCHF₂ 0 1454. H F Br Me OCHF₂ 1 1455. H F Br Me OCHF₂ 2 1456. H F Br Me CF₃ 0 1457. H F Br Me CF₃ 1 1458. H F Br Me CF₃ 2 1459. H Cl CF₃ tBu Cl 0 1460. H Cl CF₃ tBu Cl 1 1461. H Cl CF₃ tBu Cl 2 1462. H Cl CF₃ CHF₂ Cl 0 1463. H Cl CF₃ CHF₂ Cl 1 1464. H Cl CF₃ CHF₂ Cl 2 1465. H Cl Cl CHF₂ CF₃ 0 1466. H Cl Cl CHF₂ CF₃ 1 1467. H Cl Cl CHF₂ CF₃ 2 1468. H Cl CF₃ Me OMe 0 1469. H Cl CF₃ Me OMe 1 1470. H Cl CF₃ Me OMe 2 1471. H Cl CF₃ Me CN 0 1472. H Cl CF₃ Me CN 1 1473. H Cl CF₃ Me CN 2 1474. H Cl CHF₂ Me Cl 0 1475. H Cl CHF₂ Me Cl 1 1476. H Cl CHF₂ Me Cl 2 1477. H Cl Me Me Me 0 1478. H Cl Me Me Me 1 1479. H Cl Me Me Me 2 1480. H Cl Me Me Cl 0 1481. H Cl Me Me Cl 1 1482. H Cl Me Me Cl 2 1483. H Cl CF₃ Me Cl 0 1484. H Cl CF₃ Me Cl 1 1485. H Cl CF₃ Me Cl 2 1486. H Cl Cl Me CF₃ 0 1487. H Cl Cl Me CF₃ 1 1488. H Cl Cl Me CF₃ 2 1489. H Cl CF₃ Me F 0 1490. H Cl CF₃ Me F 1 1491. H Cl CF₃ Me F 2 1492. H Cl OMe Me CF₃ 0 1493. H Cl OMe Me CF₃ 1 1494. H Cl OMe Me CF₃ 2 1495. H Cl CF₃ Me OCHF₂ 0 1496. H Cl CF₃ Me OCHF₂ 1 1497. H Cl CF₃ Me OCHF₂ 2 1498. H Cl OCHF₂ Me CF₃ 0 1499. H Cl OCHF₂ Me CF₃ 1 1500. H Cl OCHF₂ Me CF₃ 2 1501. H Cl CF₃ Me OCH₂CHF₂ 0 1502. H Cl CF₃ Me OCH₂CHF₂ 1 1503. H Cl CF₃ Me OCH₂CHF₂ 2 1504. H Cl CF₃ Me OCH₂CF₃ 0 1505. H Cl CF₃ Me OCH₂CF₃ 1 1506. H Cl CF₃ Me OCH₂CF₃ 2 1507. H Cl CF₃ Me SO₂Me 0 1508. H Cl CF₃ Me SO₂Me 1 1509. H Cl CF₃ Me SO₂Me 2 1510. H Cl CF₃ Me SEt 0 1511. H Cl CF₃ Me SEt 1 1512. H Cl CF₃ Me SEt 2 1513. H Cl CF₃ Et Cl 0 1514. H Cl CF₃ Et Cl 1 1515. H Cl CF₃ Et Cl 2 1516. H Cl CF₃ iPr Cl 0 1517. H Cl CF₃ iPr Cl 1 1518. H Cl CF₃ iPr Cl 2 1519. H Cl CF₃ tBu Cl 0 1520. H Cl CF₃ tBu Cl 1 1521. H Cl CF₃ tBu Cl 2 1522. H Cl Cl tBu CF₃ 0 1523. H Cl Cl tBu CF₃ 1 1524. H Cl Cl tBu CF₃ 2 1525. H Cl CF₃ cPen Cl 0 1526. H Cl CF₃ cPen Cl 1 1527. H Cl CF₃ cPen Cl 2 1528. H Cl CF₃ CHF₂ OMe 0 1529. H Cl CF₃ CHF₂ OMe 1 1530. H Cl CF₃ CHF₂ OMe 2 1531. H Cl CF₃ CH₂CF₃ Cl 0 1532. H Cl CF₃ CH₂CF₃ Cl 1 1533. H Cl CF₃ CH₂CF₃ Cl 2 1534. H Cl CF₃ Ph OCHF₂ 0 1535. H Cl CF₃ Ph OCHF₂ 1 1536. H Cl CF₃ Ph OCHF₂ 2 1537. H Cl CF₃ Ph Cl 0 1538. H Cl CF₃ Ph Cl 1 1539. H Cl CF₃ Ph Cl 2 1540. H Cl Me Me OCH₂CF₃ 0 1541. H Cl Me Me OCH₂CF₃ 1 1542. H Cl Me Me OCH₂CF₃ 2 1543. H Cl CF₃ Me

0 1544. H Cl CF₃ Me

1 1545. H Cl CF₃ Me

2 1546. H Cl CF₃ Me H 0 1547. H Cl CF₃ Me H 1 1548. H Cl CF₃ Me H 2 1549. H Cl CF₃ Me OCH₂CH₂OMe 0 1550. H Cl CF₃ Me OCH₂CH₂OMe 1 1551. H Cl CF₃ Me OCH₂CH₂OMe 2 1552. H Cl CF₃ Me SMe 0 1553. H Cl CF₃ Me SMe 1 1554. H Cl CF₃ Me SMe 2 1555. H Cl CF₃ Me OCH₂CH₂CH₂F 0 1556. H Cl CF₃ Me OCH₂CH₂CH₂F 1 1557. H Cl CF₃ Me OCH₂CH₂CH₂F 2 1558. H Cl CF₃ Me OCH(CH₂F)₂ 0 1559. H Cl CF₃ Me OCH(CH₂F)₂ 1 1560. H Cl CF₃ Me OCH(CH₂F)₂ 2 1561. H Cl CF₃ Me OCH₂CF₂CHF₂ 0 1562. H Cl CF₃ Me OCH₂CF₂CHF₂ 1 1563. H Cl CF₃ Me OCH₂CF₂CHF₂ 2 1564. H Cl CF₃ Me OCH₂CF═CH₂ 0 1565. H Cl CF₃ Me OCH₂CF═CH₂ 1 1566. H Cl CF₃ Me OCH₂CF═CH₂ 2 1567. H Cl CF₃ Me OCH(Me)CF₃ 0 1568. H Cl CF₃ Me OCH(Me)CF₃ 1 1569. H Cl CF₃ Me OCH(Me)CF₃ 2 1570. H Cl CF₃ Me OCH(Me)CH₂F 0 1571. H Cl CF₃ Me OCH(Me)CH₂F 1 1572. H Cl CF₃ Me OCH(Me)CH₂F 2 1573. H Cl OCH₂CF₃ Me CF₃ 0 1574. H Cl OCH₂CF₃ Me CF₃ 1 1575. H Cl OCH₂CF₃ Me CF₃ 2 1576. H Cl OCH₂CF₃ Me CHF₂ 0 1577. H Cl OCH₂CF₃ Me CHF₂ 1 1578. H Cl OCH₂CF₃ Me CHF₂ 2 1579. H Cl CHF₂ Me CHF₂ 0 1580. H Cl CHF₂ Me CHF₂ 1 1581. H Cl CHF₂ Me CHF₂ 2 1582. H Cl CF₃ Me CHF₂ 0 1583. H Cl CF₃ Me CHF₂ 1 1584. H Cl CF₃ Me CHF₂ 2 1585. H Cl Cl Me OCHF₂ 0 1586. H Cl Cl Me OCHF₂ 1 1587. H Cl Cl Me OCHF₂ 2 1588. H Cl Br Me OCHF₂ 0 1589. H Cl Br Me OCHF₂ 1 1590. H Cl Br Me OCHF₂ 2 1591. H Cl Br Me CF₃ 0 1592. H Cl Br Me CF₃ 1 1593. H Cl Br Me CF₃ 2 1594. H Br CF₃ tBu Cl 0 1595. H Br CF₃ tBu Cl 1 1596. H Br CF₃ tBu Cl 2 1597. H Br CF₃ CHF₂ Cl 0 1598. H Br CF₃ CHF₂ Cl 1 1599. H Br CF₃ CHF₂ Cl 2 1600. H Br Cl CHF₂ CF₃ 0 1601. H Br Cl CHF₂ CF₃ 1 1602. H Br Cl CHF₂ CF₃ 2 1603. H Br CF₃ Me OMe 0 1604. H Br CF₃ Me OMe 1 1605. H Br CF₃ Me OMe 2 1606. H Br CF₃ Me CN 0 1607. H Br CF₃ Me CN 1 1608. H Br CF₃ Me CN 2 1609. H Br CHF₂ Me Cl 0 1610. H Br CHF₂ Me Cl 1 1611. H Br CHF₂ Me Cl 2 1612. H Br Me Me Me 0 1613. H Br Me Me Me 1 1614. H Br Me Me Me 2 1615. H Br Me Me Cl 0 1616. H Br Me Me Cl 1 1617. H Br Me Me Cl 2 1618. H Br CF₃ Me Cl 0 1619. H Br CF₃ Me Cl 1 1620. H Br CF₃ Me Cl 2 1621. H Br Cl Me CF₃ 0 1622. H Br Cl Me CF₃ 1 1623. H Br Cl Me CF₃ 2 1624. H Br CF₃ Me F 0 1625. H Br CF₃ Me F 1 1626. H Br CF₃ Me F 2 1627. H Br OMe Me CF₃ 0 1628. H Br OMe Me CF₃ 1 1629. H Br OMe Me CF₃ 2 1630. H Br CF₃ Me OCHF₂ 0 1631. H Br CF₃ Me OCHF₂ 1 1632. H Br CF₃ Me OCHF₂ 2 1633. H Br OCHF₂ Me CF₃ 0 1634. H Br OCHF₂ Me CF₃ 1 1635. H Br OCHF₂ Me CF₃ 2 1636. H Br CF₃ Me OCH₂CHF₂ 0 1637. H Br CF₃ Me OCH₂CHF₂ 1 1638. H Br CF₃ Me OCH₂CHF₂ 2 1639. H Br CF₃ Me OCH₂CF₃ 0 1640. H Br CF₃ Me OCH₂CF₃ 1 1641. H Br CF₃ Me OCH₂CF₃ 2 1642. H Br CF₃ Me SO₂Me 0 1643. H Br CF₃ Me SO₂Me 1 1644. H Br CF₃ Me SO₂Me 2 1645. H Br CF₃ Me SEt 0 1646. H Br CF₃ Me SEt 1 1647. H Br CF₃ Me SEt 2 1648. H Br CF₃ Et Cl 0 1649. H Br CF₃ Et Cl 1 1650. H Br CF₃ Et Cl 2 1651. H Br CF₃ iPr Cl 0 1652. H Br CF₃ iPr Cl 1 1653. H Br CF₃ iPr Cl 2 1654. H Br CF₃ tBu Cl 0 1655. H Br CF₃ tBu Cl 1 1656. H Br CF₃ tBu Cl 2 1657. H Br Cl tBu CF₃ 0 1658. H Br Cl tBu CF₃ 1 1659. H Br Cl tBu CF₃ 2 1660. H Br CF₃ cPen Cl 0 1661. H Br CF₃ cPen Cl 1 1662. H Br CF₃ cPen Cl 2 1663. H Br CF₃ CHF₂ OMe 0 1664. H Br CF₃ CHF₂ OMe 1 1665. H Br CF₃ CHF₂ OMe 2 1666. H Br CF₃ CH₂CF₃ Cl 0 1667. H Br CF₃ CH₂CF₃ Cl 1 1668. H Br CF₃ CH₂CF₃ Cl 2 1669. H Br CF₃ Ph OCHF₂ 0 1670. H Br CF₃ Ph OCHF₂ 1 1671. H Br CF₃ Ph OCHF₂ 2 1672. H Br CF₃ Ph Cl 0 1673. H Br CF₃ Ph Cl 1 1674. H Br CF₃ Ph Cl 2 1675. H Br Me Me OCH₂CF₃ 0 1676. H Br Me Me OCH₂CF₃ 1 1677. H Br Me Me OCH₂CF₃ 2 1678. H Br CF₃ Me

0 1679. H Br CF₃ Me

1 1680. H Br CF₃ Me

2 1681. H Br CF₃ Me H 0 1682. H Br CF₃ Me H 1 1683. H Br CF₃ Me H 2 1684. H Br CF₃ Me OCH₂CH₂OMe 0 1685. H Br CF₃ Me OCH₂CH₂OMe 1 1686. H Br CF₃ Me OCH₂CH₂OMe 2 1687. H Br CF₃ Me SMe 0 1688. H Br CF₃ Me SMe 1 1689. H Br CF₃ Me SMe 2 1690. H Br CF₃ Me OCH₂CH₂CH₂F 0 1691. H Br CF₃ Me OCH₂CH₂CH₂F 1 1692. H Br CF₃ Me OCH₂CH₂CH₂F 2 1693. H Br CF₃ Me OCH(CH₂F)₂ 0 1694. H Br CF₃ Me OCH(CH₂F)₂ 1 1695. H Br CF₃ Me OCH(CH₂F)₂ 2 1696. H Br CF₃ Me OCH₂CF₂CHF₂ 0 1697. H Br CF₃ Me OCH₂CF₂CHF₂ 1 1698. H Br CF₃ Me OCH₂CF₂CHF₂ 2 1699. H Br CF₃ Me OCH₂CF═CH₂ 0 1700. H Br CF₃ Me OCH₂CF═CH₂ 1 1701. H Br CF₃ Me OCH₂CF═CH₂ 2 1702. H Br CF₃ Me OCH(Me)CF₃ 0 1703. H Br CF₃ Me OCH(Me)CF₃ 1 1704. H Br CF₃ Me OCH(Me)CF₃ 2 1705. H Br CF₃ Me OCH(Me)CH₂F 0 1706. H Br CF₃ Me OCH(Me)CH₂F 1 1707. H Br CF₃ Me OCH(Me)CH₂F 2 1708. H Br OCH₂CF₃ Me CF₃ 0 1709. H Br OCH₂CF₃ Me CF₃ 1 1710. H Br OCH₂CF₃ Me CF₃ 2 1711. H Br OCH₂CF₃ Me CHF₂ 0 1712. H Br OCH₂CF₃ Me CHF₂ 1 1713. H Br OCH₂CF₃ Me CHF₂ 2 1714. H Br CHF₂ Me CHF₂ 0 1715. H Br CHF₂ Me CHF₂ 1 1716. H Br CHF₂ Me CHF₂ 2 1717. H Br CF₃ Me CHF₂ 0 1718. H Br CF₃ Me CHF₂ 1 1719. H Br CF₃ Me CHF₂ 2 1720. H Br Cl Me OCHF₂ 0 1721. H Br Cl Me OCHF₂ 1 1722. H Br Cl Me OCHF₂ 2 1723. H Br Br Me OCHF₂ 0 1724. H Br Br Me OCHF₂ 1 1725. H Br Br Me OCHF₂ 2 1726. H Br Br Me CF₃ 0 1727. H Br Br Me CF₃ 1 1728. H Br Br Me CF₃ 2 1729. Me H CF₃ tBu Cl 0 1730. Me H CF₃ tBu Cl 1 1731. Me H CF₃ tBu Cl 2 1732. Me H CF₃ CHF₂ Cl 0 1733. Me H CF₃ CHF₂ Cl 1 1734. Me H CF₃ CHF₂ Cl 2 1735. Me H Cl CHF₂ CF₃ 0 1736. Me H Cl CHF₂ CF₃ 1 1737. Me H Cl CHF₂ CF₃ 2 1738. Me H CF₃ Me OMe 0 1739. Me H CF₃ Me OMe 1 1740. Me H CF₃ Me OMe 2 1741. Me H CF₃ Me CN 0 1742. Me H CF₃ Me CN 1 1743. Me H CF₃ Me CN 2 1744. Me H CHF₂ Me Cl 0 1745. Me H CHF₂ Me Cl 1 1746. Me H CHF₂ Me Cl 2 1747. Me H Me Me Me 0 1748. Me H Me Me Me 1 1749. Me H Me Me Me 2 1750. Me H Me Me Cl 0 1751. Me H Me Me Cl 1 1752. Me H Me Me Cl 2 1753. Me H CF₃ Me Cl 0 1754. Me H CF₃ Me Cl 1 1755. Me H CF₃ Me Cl 2 1756. Me H Cl Me CF₃ 0 1757. Me H Cl Me CF₃ 1 1758. Me H Cl Me CF₃ 2 1759. Me H CF₃ Me F 0 1760. Me H CF₃ Me F 1 1761. Me H CF₃ Me F 2 1762. Me H OMe Me CF₃ 0 1763. Me H OMe Me CF₃ 1 1764. Me H OMe Me CF₃ 2 1765. Me H CF₃ Me OCHF₂ 0 1766. Me H CF₃ Me OCHF₂ 1 1767. Me H CF₃ Me OCHF₂ 2 1768. Me H OCHF₂ Me CF₃ 0 1769. Me H OCHF₂ Me CF₃ 1 1770. Me H OCHF₂ Me CF₃ 2 1771. Me H CF₃ Me OCH₂CHF₂ 0 1772. Me H CF₃ Me OCH₂CHF₂ 1 1773. Me H CF₃ Me OCH₂CHF₂ 2 1774. Me H CF₃ Me OCH₂CF₃ 0 1775. Me H CF₃ Me OCH₂CF₃ 1 1776. Me H CF₃ Me OCH₂CF₃ 2 1777. Me H CF₃ Me SO₂Me 0 1778. Me H CF₃ Me SO₂Me 1 1779. Me H CF₃ Me SO₂Me 2 1780. Me H CF₃ Me SEt 0 1781. Me H CF₃ Me SEt 1 1782. Me H CF₃ Me SEt 2 1783. Me H CF₃ Et Cl 0 1784. Me H CF₃ Et Cl 1 1785. Me H CF₃ Et Cl 2 1786. Me H CF₃ iPr Cl 0 1787. Me H CF₃ iPr Cl 1 1788. Me H CF₃ iPr Cl 2 1789. Me H CF₃ tBu Cl 0 1790. Me H CF₃ tBu Cl 1 1791. Me H CF₃ tBu Cl 2 1792. Me H Cl tBu CF₃ 0 1793. Me H Cl tBu CF₃ 1 1794. Me H Cl tBu CF₃ 2 1795. Me H CF₃ cPen Cl 0 1796. Me H CF₃ cPen Cl 1 1797. Me H CF₃ cPen Cl 2 1798. Me H CF₃ CHF₂ OMe 0 1799. Me H CF₃ CHF₂ OMe 1 1800. Me H CF₃ CHF₂ OMe 2 1801. Me H CF₃ CH₂CF₃ Cl 0 1802. Me H CF₃ CH₂CF₃ Cl 1 1803. Me H CF₃ CH₂CF₃ Cl 2 1804. Me H CF₃ Ph OCHF₂ 0 1805. Me H CF₃ Ph OCHF₂ 1 1806. Me H CF₃ Ph OCHF₂ 2 1807. Me H CF₃ Ph Cl 0 1808. Me H CF₃ Ph Cl 1 1809. Me H CF₃ Ph Cl 2 1810. Me H Me Me OCH₂CF₃ 0 1811. Me H Me Me OCH₂CF₃ 1 1812. Me H Me Me OCH₂CF₃ 2 1813. Me H CF₃ Me

0 1814. Me H CF₃ Me

1 1815. Me H CF₃ Me

2 1816. Me H CF₃ Me H 0 1817. Me H CF₃ Me H 1 1818. Me H CF₃ Me H 2 1819. Me H CF₃ Me OCH₂CH₂OMe 0 1820. Me H CF₃ Me OCH₂CH₂OMe 1 1821. Me H CF₃ Me OCH₂CH₂OMe 2 1822. Me H CF₃ Me SMe 0 1823. Me H CF₃ Me SMe 1 1824. Me H CF₃ Me SMe 2 1825. Me H CF₃ Me OCH₂CH₂CH₂F 0 1826. Me H CF₃ Me OCH₂CH₂CH₂F 1 1827. Me H CF₃ Me OCH₂CH₂CH₂F 2 1828. Me H CF₃ Me OCH(CH₂F)₂ 0 1829. Me H CF₃ Me OCH(CH₂F)₂ 1 1830. Me H CF₃ Me OCH(CH₂F)₂ 2 1831. Me H CF₃ Me OCH₂CF₂CHF₂ 0 1832. Me H CF₃ Me OCH₂CF₂CHF₂ 1 1833. Me H CF₃ Me OCH₂CF₂CHF₂ 2 1834. Me H CF₃ Me OCH₂CF═CH₂ 0 1835. Me H CF₃ Me OCH₂CF═CH₂ 1 1836. Me H CF₃ Me OCH₂CF═CH₂ 2 1837. Me H CF₃ Me OCH(Me)CF₃ 0 1838. Me H CF₃ Me OCH(Me)CF₃ 1 1839. Me H CF₃ Me OCH(Me)CF₃ 2 1840. Me H CF₃ Me OCH(Me)CH₂F 0 1841. Me H CF₃ Me OCH(Me)CH₂F 1 1842. Me H CF₃ Me OCH(Me)CH₂F 2 1843. Me H OCH₂CF₃ Me CF₃ 0 1844. Me H OCH₂CF₃ Me CF₃ 1 1845. Me H OCH₂CF₃ Me CF₃ 2 1846. Me H OCH₂CF₃ Me CHF₂ 0 1847. Me H OCH₂CF₃ Me CHF₂ 1 1848. Me H OCH₂CF₃ Me CHF₂ 2 1849. Me H CHF₂ Me CHF₂ 0 1850. Me H CHF₂ Me CHF₂ 1 1851. Me H CHF₂ Me CHF₂ 2 1852. Me H CF₃ Me CHF₂ 0 1853. Me H CF₃ Me CHF₂ 1 1854. Me H CF₃ Me CHF₂ 2 1855. Me H Cl Me OCHF₂ 0 1856. Me H Cl Me OCHF₂ 1 1857. Me H Cl Me OCHF₂ 2 1858. Me H Br Me OCHF₂ 0 1859. Me H Br Me OCHF₂ 1 1860. Me H Br Me OCHF₂ 2 1861. Me H Br Me CF₃ 0 1862. Me H Br Me CF₃ 1 1863. Me H Br Me CF₃ 2 1864. NO₂ H CF₃ tBu Cl 0 1865. NO₂ H CF₃ tBu Cl 1 1866. NO₂ H CF₃ tBu Cl 2 1867. NO₂ H CF₃ CHF₂ Cl 0 1868. NO₂ H CF₃ CHF₂ Cl 1 1869. NO₂ H CF₃ CHF₂ Cl 2 1870. NO₂ H Cl CHF₂ CF₃ 0 1871. NO₂ H Cl CHF₂ CF₃ 1 1872. NO₂ H Cl CHF₂ CF₃ 2 1873. NO₂ H CF₃ Me OMe 0 1874. NO₂ H CF₃ Me OMe 1 1875. NO₂ H CF₃ Me OMe 2 1876. NO₂ H CF₃ Me CN 0 1877. NO₂ H CF₃ Me CN 1 1878. NO₂ H CF₃ Me CN 2 1879. NO₂ H CHF₂ Me Cl 0 1880. NO₂ H CHF₂ Me Cl 1 1881. NO₂ H CHF₂ Me Cl 2 1882. NO₂ H Me Me Me 0 1883. NO₂ H Me Me Me 1 1884. NO₂ H Me Me Me 2 1885. NO₂ H Me Me Cl 0 1886. NO₂ H Me Me Cl 1 1887. NO₂ H Me Me Cl 2 1888. NO₂ H CF₃ Me Cl 0 1889. NO₂ H CF₃ Me Cl 1 1890. NO₂ H CF₃ Me Cl 2 1891. NO₂ H Cl Me CF₃ 0 1892. NO₂ H Cl Me CF₃ 1 1893. NO₂ H Cl Me CF₃ 2 1894. NO₂ H CF₃ Me F 0 1895. NO₂ H CF₃ Me F 1 1896. NO₂ H CF₃ Me F 2 1897. NO₂ H OMe Me CF₃ 0 1898. NO₂ H OMe Me CF₃ 1 1899. NO₂ H OMe Me CF₃ 2 1900. NO₂ H CF₃ Me OCHF₂ 0 1901. NO₂ H CF₃ Me OCHF₂ 1 1902. NO₂ H CF₃ Me OCHF₂ 2 1903. NO₂ H OCHF₂ Me CF₃ 0 1904. NO₂ H OCHF₂ Me CF₃ 1 1905. NO₂ H OCHF₂ Me CF₃ 2 1906. NO₂ H CF₃ Me OCH₂CHF₂ 0 1907. NO₂ H CF₃ Me OCH₂CHF₂ 1 1908. NO₂ H CF₃ Me OCH₂CHF₂ 2 1909. NO₂ H CF₃ Me OCH₂CF₃ 0 1910. NO₂ H CF₃ Me OCH₂CF₃ 1 1911. NO₂ H CF₃ Me OCH₂CF₃ 2 1912. NO₂ H CF₃ Me SO₂Me 0 1913. NO₂ H CF₃ Me SO₂Me 1 1914. NO₂ H CF₃ Me SO₂Me 2 1915. NO₂ H CF₃ Me SEt 0 1916. NO₂ H CF₃ Me SEt 1 1917. NO₂ H CF₃ Me SEt 2 1918. NO₂ H CF₃ Et Cl 0 1919. NO₂ H CF₃ Et Cl 1 1920. NO₂ H CF₃ Et Cl 2 1921. NO₂ H CF₃ iPr Cl 0 1922. NO₂ H CF₃ iPr Cl 1 1923. NO₂ H CF₃ iPr Cl 2 1924. NO₂ H CF₃ tBu Cl 0 1925. NO₂ H CF₃ tBu Cl 1 1926. NO₂ H CF₃ tBu Cl 2 1927. NO₂ H Cl tBu CF₃ 0 1928. NO₂ H Cl tBu CF₃ 1 1929. NO₂ H Cl tBu CF₃ 2 1930. NO₂ H CF₃ cPen Cl 0 1931. NO₂ H CF₃ cPen Cl 1 1932. NO₂ H CF₃ cPen Cl 2 1933. NO₂ H CF₃ CHF₂ OMe 0 1934. NO₂ H CF₃ CHF₂ OMe 1 1935. NO₂ H CF₃ CHF₂ OMe 2 1936. NO₂ H CF₃ CH₂CF₃ Cl 0 1937. NO₂ H CF₃ CH₂CF₃ Cl 1 1938. NO₂ H CF₃ CH₂CF₃ Cl 2 1939. NO₂ H CF₃ Ph OCHF₂ 0 1940. NO₂ H CF₃ Ph OCHF₂ 1 1941. NO₂ H CF₃ Ph OCHF₂ 2 1942. NO₂ H CF₃ Ph Cl 0 1943. NO₂ H CF₃ Ph Cl 1 1944. NO₂ H CF₃ Ph Cl 2 1945. NO₂ H Me Me OCH₂CF₃ 0 1946. NO₂ H Me Me OCH₂CF₃ 1 1947. NO₂ H Me Me OCH₂CF₃ 2 1948. NO₂ H CF₃ Me

0 1949. NO₂ H CF₃ Me

1 1950. NO₂ H CF₃ Me

2 1951. NO₂ H CF₃ Me H 0 1952. NO₂ H CF₃ Me H 1 1953. NO₂ H CF₃ Me H 2 1954. NO₂ H CF₃ Me OCH₂CH₂OMe 0 1955. NO₂ H CF₃ Me OCH₂CH₂OMe 1 1956. NO₂ H CF₃ Me OCH₂CH₂OMe 2 1957. NO₂ H CF₃ Me SMe 0 1958. NO₂ H CF₃ Me SMe 1 1959. NO₂ H CF₃ Me SMe 2 1960. NO₂ H CF₃ Me OCH₂CH₂CH₂F 0 1961. NO₂ H CF₃ Me OCH₂CH₂CH₂F 1 1962. NO₂ H CF₃ Me OCH₂CH₂CH₂F 2 1963. NO₂ H CF₃ Me OCH(CH₂F)₂ 0 1964. NO₂ H CF₃ Me OCH(CH₂F)₂ 1 1965. NO₂ H CF₃ Me OCH(CH₂F)₂ 2 1966. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 0 1967. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 1 1968. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 2 1969. NO₂ H CF₃ Me OCH₂CF═CH₂ 0 1970. NO₂ H CF₃ Me OCH₂CF═CH₂ 1 1971. NO₂ H CF₃ Me OCH₂CF═CH₂ 2 1972. NO₂ H CF₃ Me OCH(Me)CF₃ 0 1973. NO₂ H CF₃ Me OCH(Me)CF₃ 1 1974. NO₂ H CF₃ Me OCH(Me)CF₃ 2 1975. NO₂ H CF₃ Me OCH(Me)CH₂F 0 1976. NO₂ H CF₃ Me OCH(Me)CH₂F 1 1977. NO₂ H CF₃ Me OCH(Me)CH₂F 2 1978. NO₂ H OCH₂CF₃ Me CF₃ 0 1979. NO₂ H OCH₂CF₃ Me CF₃ 1 1980. NO₂ H OCH₂CF₃ Me CF₃ 2 1981. NO₂ H OCH₂CF₃ Me CHF₂ 0 1982. NO₂ H OCH₂CF₃ Me CHF₂ 1 1983. NO₂ H OCH₂CF₃ Me CHF₂ 2 1984. NO₂ H CHF₂ Me CHF₂ 0 1985. NO₂ H CHF₂ Me CHF₂ 1 1986. NO₂ H CHF₂ Me CHF₂ 2 1987. NO₂ H CF₃ Me CHF₂ 0 1988. NO₂ H CF₃ Me CHF₂ 1 1989. NO₂ H CF₃ Me CHF₂ 2 1990. NO₂ H Cl Me OCHF₂ 0 1991. NO₂ H Cl Me OCHF₂ 1 1992. NO₂ H Cl Me OCHF₂ 2 1993. NO₂ H Br Me OCHF₂ 0 1994. NO₂ H Br Me OCHF₂ 1 1995. NO₂ H Br Me OCHF₂ 2 1996. NO₂ H Br Me CF₃ 0 1997. NO₂ H Br Me CF₃ 1 1998. NO₂ H Br Me CF₃ 2 1999. Cl Cl CF₃ tBu Cl 0 2000. Cl Cl CF₃ tBu Cl 1 2001. Cl Cl CF₃ tBu Cl 2 2002. Cl Cl CF₃ CHF₂ Cl 0 2003. Cl Cl CF₃ CHF₂ Cl 1 2004. Cl Cl CF₃ CHF₂ Cl 2 2005. Cl Cl Cl CHF₂ CF₃ 0 2006. Cl Cl Cl CHF₂ CF₃ 1 2007. Cl Cl Cl CHF₂ CF₃ 2 2008. Cl Cl CF₃ Me OMe 0 2009. Cl Cl CF₃ Me OMe 1 2010. Cl Cl CF₃ Me OMe 2 2011. Cl Cl CF₃ Me CN 0 2012. Cl Cl CF₃ Me CN 1 2013. Cl Cl CF₃ Me CN 2 2014. Cl Cl CHF₂ Me Cl 0 2015. Cl Cl CHF₂ Me Cl 1 2016. Cl Cl CHF₂ Me Cl 2 2017. Cl Cl Me Me Me 0 2018. Cl Cl Me Me Me 1 2019. Cl Cl Me Me Me 2 2020. Cl Cl Me Me Cl 0 2021. Cl Cl Me Me Cl 1 2022. Cl Cl Me Me Cl 2 2023. Cl Cl CF₃ Me Cl 0 2024. Cl Cl CF₃ Me Cl 1 2025. Cl Cl CF₃ Me Cl 2 2026. Cl Cl Cl Me CF₃ 0 2027. Cl Cl Cl Me CF₃ 1 2028. Cl Cl Cl Me CF₃ 2 2029. Cl Cl CF₃ Me F 0 2030. Cl Cl CF₃ Me F 1 2031. Cl Cl CF₃ Me F 2 2032. Cl Cl OMe Me CF₃ 0 2033. Cl Cl OMe Me CF₃ 1 2034. Cl Cl OMe Me CF₃ 2 2035. Cl Cl CF₃ Me OCHF₂ 0 2036. Cl Cl CF₃ Me OCHF₂ 1 2037. Cl Cl CF₃ Me OCHF₂ 2 2038. Cl Cl OCHF₂ Me CF₃ 0 2039. Cl Cl OCHF₂ Me CF₃ 1 2040. Cl Cl OCHF₂ Me CF₃ 2 2041. Cl Cl CF₃ Me OCH₂CHF₂ 0 2042. Cl Cl CF₃ Me OCH₂CHF₂ 1 2043. Cl Cl CF₃ Me OCH₂CHF₂ 2 2044. Cl Cl CF₃ Me OCH₂CF₃ 0 2045. Cl Cl CF₃ Me OCH₂CF₃ 1 2046. Cl Cl CF₃ Me OCH₂CF₃ 2 2047. Cl Cl CF₃ Me SO₂Me 0 2048. Cl Cl CF₃ Me SO₂Me 1 2049. Cl Cl CF₃ Me SO₂Me 2 2050. Cl Cl CF₃ Me SEt 0 2051. Cl Cl CF₃ Me SEt 1 2052. Cl Cl CF₃ Me SEt 2 2053. Cl Cl CF₃ Et Cl 0 2054. Cl Cl CF₃ Et Cl 1 2055. Cl Cl CF₃ Et Cl 2 2056. Cl Cl CF₃ iPr Cl 0 2057. Cl Cl CF₃ iPr Cl 1 2058. Cl Cl CF₃ iPr Cl 2 2059. Cl Cl CF₃ tBu Cl 0 2060. Cl Cl CF₃ tBu Cl 1 2061. Cl Cl CF₃ tBu Cl 2 2062. Cl Cl Cl tBu CF₃ 0 2063. Cl Cl Cl tBu CF₃ 1 2064. Cl Cl Cl tBu CF₃ 2 2065. Cl Cl CF₃ cPen Cl 0 2066. Cl Cl CF₃ cPen Cl 1 2067. Cl Cl CF₃ cPen Cl 2 2068. Cl Cl CF₃ CHF₂ OMe 0 2069. Cl Cl CF₃ CHF₂ OMe 1 2070. Cl Cl CF₃ CHF₂ OMe 2 2071. Cl Cl CF₃ CH₂CF₃ Cl 0 2072. Cl Cl CF₃ CH₂CF₃ Cl 1 2073. Cl Cl CF₃ CH₂CF₃ Cl 2 2074. Cl Cl CF₃ Ph OCHF₂ 0 2075. Cl Cl CF₃ Ph OCHF₂ 1 2076. Cl Cl CF₃ Ph OCHF₂ 2 2077. Cl Cl CF₃ Ph Cl 0 2078. Cl Cl CF₃ Ph Cl 1 2079. Cl Cl CF₃ Ph Cl 2 2080. Cl Cl Me Me OCH₂CF₃ 0 2081. Cl Cl Me Me OCH₂CF₃ 1 2082. Cl Cl Me Me OCH₂CF₃ 2 2083. Cl Cl CF₃ Me

0 2084. Cl Cl CF₃ Me

1 2085. Cl Cl CF₃ Me

2 2086. Cl Cl CF₃ Me H 0 2087. Cl Cl CF₃ Me H 1 2088. Cl Cl CF₃ Me H 2 2089. Cl Cl CF₃ Me OCH₂CH₂OMe 0 2090. Cl Cl CF₃ Me OCH₂CH₂OMe 1 2091. Cl Cl CF₃ Me OCH₂CH₂OMe 2 2092. Cl Cl CF₃ Me SMe 0 2093. Cl Cl CF₃ Me SMe 1 2094. Cl Cl CF₃ Me SMe 2 2095. Cl Cl CF₃ Me OCH₂CH₂CH₂F 0 2096. Cl Cl CF₃ Me OCH₂CH₂CH₂F 1 2097. Cl Cl CF₃ Me OCH₂CH₂CH₂F 2 2098. Cl Cl CF₃ Me OCH(CH₂F)₂ 0 2099. Cl Cl CF₃ Me OCH(CH₂F)₂ 1 2100. Cl Cl CF₃ Me OCH(CH₂F)₂ 2 2101. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 0 2102. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 1 2103. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 2 2104. Cl Cl CF₃ Me OCH₂CF═CH₂ 0 2105. Cl Cl CF₃ Me OCH₂CF═CH₂ 1 2106. Cl Cl CF₃ Me OCH₂CF═CH₂ 2 2107. Cl Cl CF₃ Me OCH(Me)CF₃ 0 2108. Cl Cl CF₃ Me OCH(Me)CF₃ 1 2109. Cl Cl CF₃ Me OCH(Me)CF₃ 2 2110. Cl Cl CF₃ Me OCH(Me)CH₂F 0 2111. Cl Cl CF₃ Me OCH(Me)CH₂F 1 2112. Cl Cl CF₃ Me OCH(Me)CH₂F 2 2113. Cl Cl OCH₂CF₃ Me CF₃ 0 2114. Cl Cl OCH₂CF₃ Me CF₃ 1 2115. Cl Cl OCH₂CF₃ Me CF₃ 2 2116. Cl Cl OCH₂CF₃ Me CHF₂ 0 2117. Cl Cl OCH₂CF₃ Me CHF₂ 1 2118. Cl Cl OCH₂CF₃ Me CHF₂ 2 2119. Cl Cl CHF₂ Me CHF₂ 0 2120. Cl Cl CHF₂ Me CHF₂ 1 2121. Cl Cl CHF₂ Me CHF₂ 2 2122. Cl Cl CF₃ Me CHF₂ 0 2123. Cl Cl CF₃ Me CHF₂ 1 2124. Cl Cl CF₃ Me CHF₂ 2 2125. Cl Cl Cl Me OCHF₂ 0 2126. Cl Cl Cl Me OCHF₂ 1 2127. Cl Cl Cl Me OCHF₂ 2 2128. Cl Cl Br Me OCHF₂ 0 2129. Cl Cl Br Me OCHF₂ 1 2130. Cl Cl Br Me OCHF₂ 2 2131. Cl Cl Br Me CF₃ 0 2132. Cl Cl Br Me CF₃ 1 2133. Cl Cl Br Me CF₃ 2 2134. Cl Me CF₃ tBu Cl 0 2135. Cl Me CF₃ tBu Cl 1 2136. Cl Me CF₃ tBu Cl 2 2137. Cl Me CF₃ CHF₂ Cl 0 2138. Cl Me CF₃ CHF₂ Cl 1 2139. Cl Me CF₃ CHF₂ Cl 2 2140. Cl Me Cl CHF₂ CF₃ 0 2141. Cl Me Cl CHF₂ CF₃ 1 2142. Cl Me Cl CHF₂ CF₃ 2 2143. Cl Me CF₃ Me OMe 0 2144. Cl Me CF₃ Me OMe 1 2145. Cl Me CF₃ Me OMe 2 2146. Cl Me CF₃ Me CN 0 2147. Cl Me CF₃ Me CN 1 2148. Cl Me CF₃ Me CN 2 2149. Cl Me CHF₂ Me Cl 0 2150. Cl Me CHF₂ Me Cl 1 2151. Cl Me CHF₂ Me Cl 2 2152. Cl Me Me Me Me 0 2153. Cl Me Me Me Me 1 2154. Cl Me Me Me Me 2 2155. Cl Me Me Me Cl 0 2156. Cl Me Me Me Cl 1 2157. Cl Me Me Me Cl 2 2158. Cl Me CF₃ Me Cl 0 2159. Cl Me CF₃ Me Cl 1 2160. Cl Me CF₃ Me Cl 2 2161. Cl Me Cl Me CF₃ 0 2162. Cl Me Cl Me CF₃ 1 2163. Cl Me Cl Me CF₃ 2 2164. Cl Me CF₃ Me F 0 2165. Cl Me CF₃ Me F 1 2166. Cl Me CF₃ Me F 2 2167. Cl Me OMe Me CF₃ 0 2168. Cl Me OMe Me CF₃ 1 2169. Cl Me OMe Me CF₃ 2 2170. Cl Me CF₃ Me OCHF₂ 0 2171. Cl Me CF₃ Me OCHF₂ 1 2172. Cl Me CF₃ Me OCHF₂ 2 2173. Cl Me OCHF₂ Me CF₃ 0 2174. Cl Me OCHF₂ Me CF₃ 1 2175. Cl Me OCHF₂ Me CF₃ 2 2176. Cl Me CF₃ Me OCH₂CHF₂ 0 2177. Cl Me CF₃ Me OCH₂CHF₂ 1 2178. Cl Me CF₃ Me OCH₂CHF₂ 2 2179. Cl Me CF₃ Me OCH₂CF₃ 0 2180. Cl Me CF₃ Me OCH₂CF₃ 1 2181. Cl Me CF₃ Me OCH₂CF₃ 2 2182. Cl Me CF₃ Me SO₂Me 0 2183. Cl Me CF₃ Me SO₂Me 1 2184. Cl Me CF₃ Me SO₂Me 2 2185. Cl Me CF₃ Me SEt 0 2186. Cl Me CF₃ Me SEt 1 2187. Cl Me CF₃ Me SEt 2 2188. Cl Me CF₃ Et Cl 0 2189. Cl Me CF₃ Et Cl 1 2190. Cl Me CF₃ Et Cl 2 2191. Cl Me CF₃ iPr Cl 0 2192. Cl Me CF₃ iPr Cl 1 2193. Cl Me CF₃ iPr Cl 2 2194. Cl Me CF₃ tBu Cl 0 2195. Cl Me CF₃ tBu Cl 1 2196. Cl Me CF₃ tBu Cl 2 2197. Cl Me Cl tBu CF₃ 0 2198. Cl Me Cl tBu CF₃ 1 2199. Cl Me Cl tBu CF₃ 2 2200. Cl Me CF₃ cPen Cl 0 2201. Cl Me CF₃ cPen Cl 1 2202. Cl Me CF₃ cPen Cl 2 2203. Cl Me CF₃ CHF₂ OMe 0 2204. Cl Me CF₃ CHF₂ OMe 1 2205. Cl Me CF₃ CHF₂ OMe 2 2206. Cl Me CF₃ CH₂CF₃ Cl 0 2207. Cl Me CF₃ CH₂CF₃ Cl 1 2208. Cl Me CF₃ CH₂CF₃ Cl 2 2209. Cl Me CF₃ Ph OCHF₂ 0 2210. Cl Me CF₃ Ph OCHF₂ 1 2211. Cl Me CF₃ Ph OCHF₂ 2 2212. Cl Me CF₃ Ph Cl 0 2213. Cl Me CF₃ Ph Cl 1 2214. Cl Me CF₃ Ph Cl 2 2215. Cl Me Me Me OCH₂CF₃ 0 2216. Cl Me Me Me OCH₂CF₃ 1 2217. Cl Me Me Me OCH₂CF₃ 2 2218. Cl Me CF₃ Me

0 2219. Cl Me CF₃ Me

1 2220. Cl Me CF₃ Me

2 2221. Cl Me CF₃ Me H 0 2222. Cl Me CF₃ Me H 1 2223. Cl Me CF₃ Me H 2 2224. Cl Me CF₃ Me OCH₂CH₂OMe 0 2225. Cl Me CF₃ Me OCH₂CH₂OMe 1 2226. Cl Me CF₃ Me OCH₂CH₂OMe 2 2227. Cl Me CF₃ Me SMe 0 2228. Cl Me CF₃ Me SMe 1 2229. Cl Me CF₃ Me SMe 2 2230. Cl Me CF₃ Me OCH₂CH₂CH₂F 0 2231. Cl Me CF₃ Me OCH₂CH₂CH₂F 1 2232. Cl Me CF₃ Me OCH₂CH₂CH₂F 2 2233. Cl Me CF₃ Me OCH(CH₂F)₂ 0 2234. Cl Me CF₃ Me OCH(CH₂F)₂ 1 2235. Cl Me CF₃ Me OCH(CH₂F)₂ 2 2236. Cl Me CF₃ Me OCH₂CF₂CHF₂ 0 2237. Cl Me CF₃ Me OCH₂CF₂CHF₂ 1 2238. Cl Me CF₃ Me OCH₂CF₂CHF₂ 2 2239. Cl Me CF₃ Me OCH₂CF═CH₂ 0 2240. Cl Me CF₃ Me OCH₂CF═CH₂ 1 2241. Cl Me CF₃ Me OCH₂CF═CH₂ 2 2242. Cl Me CF₃ Me OCH(Me)CF₃ 0 2243. Cl Me CF₃ Me OCH(Me)CF₃ 1 2244. Cl Me CF₃ Me OCH(Me)CF₃ 2 2245. Cl Me CF₃ Me OCH(Me)CH₂F 0 2246. Cl Me CF₃ Me OCH(Me)CH₂F 1 2247. Cl Me CF₃ Me OCH(Me)CH₂F 2 2248. Cl Me OCH₂CF₃ Me CF₃ 0 2249. Cl Me OCH₂CF₃ Me CF₃ 1 2250. Cl Me OCH₂CF₃ Me CF₃ 2 2251. Cl Me OCH₂CF₃ Me CHF₂ 0 2252. Cl Me OCH₂CF₃ Me CHF₂ 1 2253. Cl Me OCH₂CF₃ Me CHF₂ 2 2254. Cl Me CHF₂ Me CHF₂ 0 2255. Cl Me CHF₂ Me CHF₂ 1 2256. Cl Me CHF₂ Me CHF₂ 2 2257. Cl Me CF₃ Me CHF₂ 0 2258. Cl Me CF₃ Me CHF₂ 1 2259. Cl Me CF₃ Me CHF₂ 2 2260. Cl Me Cl Me OCHF₂ 0 2261. Cl Me Cl Me OCHF₂ 1 2262. Cl Me Cl Me OCHF₂ 2 2263. Cl Me Br Me OCHF₂ 0 2264. Cl Me Br Me OCHF₂ 1 2265. Cl Me Br Me OCHF₂ 2 2266. Cl Me Br Me CF₃ 0 2267. Cl Me Br Me CF₃ 1 2268. Cl Me Br Me CF₃ 2

NMR data of selected compounds of Table 1:

5-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 542: NMR (CDCl₃, 400 MHz): 3.87 (s, 3H, CH₃); 4.38 (d, 1H, S(O)CH₂); 4.50 (d, 1H, S(O)CH₂); 6.92 (dd, 1H, OCHF₂); 7.16 (s, 1H).

5-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 543: NMR (CDCl₃, 400 MHz): 3.88 (s, 3H, CH₃); 4.59 (s, 2H, S(O)₂CH₂); 6.81 (t, 1H, OCHF₂); 7.19 (s, 1H).

5-Bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 788: NMR (CDCl₃, 400 MHz): 3.85 (s, 3H, CH₃); 4.38 (d, 1H, S(O)CH₂); 4.49 (d, 1H, S(O)CH₂); 6.91 (dd, 1H, OCHF₂); 7.24 (s, 1H).

5-Bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 789: NMR (CDCl₃, 400 MHz): 3.88 (s, 3H, CH₃); 4.59 (s, 2H, S(O)₂CH₂); 6.81 (t, 1H, OCHF₂); 7.28 (s, 1H).

5-Iodo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 1034: NMR (CDCl₃, 400 MHz): 3.85 (s, 3H, CH₃); 4.37 (d, 1H, S(O)CH₂); 4.48 (d, 1H, S(O)CH₂); 6.92 (dd, 1H, OCHF₂); 7.38 (s, 1H).

5-Iodo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 1035: NMR (CDCl₃, 400 MHz): 3.88 (s, 3H, CH₃); 4.59 (s, 2H, S(O)₂CH₂); 6.81 (t, 1H, OCHF₂); 7.40 (s, 1H).

2-({[5-(Chloro)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 35: NMR (CDCl₃, 400 MHz): 4.00 (s, 3H, CH₃); 4.50 (br s, 2H, S(O)CH₂); 7.36 (br d, 1H); 7.91 (br d, 1H).

2-({[5-(Chloro)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 36: NMR (CDCl₃, 400 MHz): 3.20 (s, 3H, CH₃); 4.61 (s, 2H, S(O)₂CH₂); 7.40 (br d, 1H); 7.89 (br d, 1H).

2-({[3-(Difluoromethyl)-1-methyl-5-(2,2,2-trifluoroethoxy)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 242: NMR (CDCl₃, 400 MHz): 3.75 (s, 3H, CH₃); 4.41 (d, 1H, S(O)CH₂); 4.51 (d, 1H, S(O)CH₂); 4.74 (d×q, 1H); 4.78 (d×q, 1H); 6.57 (t, 1H); 7.39 (br d, 1H); 7.93 (br d, 1H).

2-({[1-Methyl-3,5-bis(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 230: NMR (CDCl₃, 400 MHz): 4.09 (s, 3H, CH₃); 4.55 (d, 1H, S(O)CH₂); 4.66 (d, 1H, S(O)CH₂); 7.36 (br d, 1H); 7.93 (br d, 1H).

2-({[3-(Difluoromethyl)-1-methyl-5-(2,2,2-trifluoroethoxy)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

Compound No. 241: NMR (CDCl₃, 400 MHz): 3.71 (s, 3H, CH₃); 4.39 (s, 2H, SCH₂); 4.63 (q, 2H); 5.60 (t, 1H); 7.11 (br d, 1H); 7.69 (br d, 1H).

2-({[3-(Difluoromethyl)-1-methyl-5-(2,2,2-trifluoroethoxy)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 243: NMR (CDCl₃, 400 MHz): 3.78 (s, 3H, CH₃); 4.62 (s, 2H, S(O)₂CH₂); 4.69 (q, 2H); 6.54 (t, 1H); 7.39 (br d, 1H); 7.89 (br d, 1H).

2-({[1-Methyl-3,5-bis(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 231: NMR (CDCl₃, 400 MHz): 4.10 (s, 3H, CH₃); 4.26 (s, 2H, S(O)₂CH₂); 7.41 (br d, 1H); 7.89 (br d, 1H).

2-({[1-Methyl-3,5-bis(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

Compound No. 229: NMR (CDCl₃, 400 MHz): 4.05 (s, 3H, CH₃); 4.43 (s, 2H, SCH₂); 7.15 (br d, 1H); 7.69 (br d, 1H).

2-({[5-(Difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

Compound No. 217: NMR (CDCl₃, 400 MHz): 4.02 (s, 3H, CH₃); 4.33 (s, 2H, SCH₂); 7.11 (br d, 1H); 7.31 (t, 1H); 7.65 (br d, 1H).

2-({[5-(Difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 218: NMR (CDCl₃, 400 MHz): 4.10 (s, 3H, CH₃); 4.51 (d, 1H, S(O)CH₂); 4.56 (d, 1H, S(O)CH₂); 6.97 (t, 1H); 7.38 (br d, 1H); 7.90 (br d, 1H).

2-({[5-(Difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 219: NMR (CDCl₃, 400 MHz): 4.10 (s, 3H, CH₃); 4.70 (s, 2H, S(O)₂CH₂); 7.02 (t, 1H); 7.39 (br d, 1H); 7.88 (br d, 1H).

2-({[1-Methyl-5-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

Compound No. 58: NMR (CDCl₃, 400 MHz): 3.75 (s, 3H, CH₃); 4.36 (s, 2H, SCH₂); 4.67 (q, 2H); 7.12 (br d, 1H); 7.69 (br d, 1H).

2-({[1-Methyl-5-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 59: NMR (CDCl₃, 400 MHz): 3.80 (s, 3H, CH₃); 4.31 (d, 1H, S(O)CH₂); 4.52 (d, 1H, S(O)CH₂); 4.76 (q, 1H); 4.78 (q, 1H); 7.40 (br d, 1H); 7.93 (br d, 1H).

2-({[1-Methyl-5-(2,2,2-trifluoroethoxy)-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-1,3-oxazole

Compound No. 60: NMR (CDCl₃, 400 MHz): 3.82 (s, 3H, CH₃); 4.60 (s, 2H, S(O)₂CH₂); 4.72 (q, 2H); 7.41 (br d, 1H); 7.90 (br d, 1H).

4-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-oxazole

Compound No. 1495: NMR (CDCl₃, 400 MHz): 3.80 (s, 3H, CH₃); 4.32 (s, 2H, SCH₂); 6.76 (t, 1H); 7.61 (br d, 1H).

4-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-oxazole

Compound No. 1496: NMR (CDCl₃, 400 MHz): 3.85 (s, 3H, CH₃); 4.39 (d, 1H, S(O)CH₂); 4.48 (d, 1H, S(O)CH₂); 6.90 (dxt, 1H); 7.82 (br d, 1H).

5-Chloro-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-4-methyl-1,3-oxazole

Compound No. 2170: NMR (CDCl₃, 400 MHz): 2.09 (s, 3H, CH₃); 3.81 (s, 3H, CH₃); 4.25 (s, 2H, SCH₂); 6.74 (t, 1H).

TABLE 2 Compounds of the formula (III-S) (III-S)

Ex. No. R¹ R² R³ R⁴ R⁵ 2269. H H CF₃ Ph Cl 2270. H H CF₃ tBu Cl 2271. H H CF₃ CHF₂ Cl 2272. H H Cl CHF₂ CF₃ 2273. H H CF₃ Me OMe 2274. H H CF₃ Me CN 2275. H H Cl Et Cl 2276. H H CHF₂ Me Cl 2277. H H Me Me Me 2278. H H Me Me Cl 2279. H H Cl Me Cl 2280. H H CF₃ Me Cl 2281. H H Cl Me CF₃ 2282. H H CF₃ Me F 2283. H H OMe Me CF₃ 2284. H H CF₃ Me OEt 2285. H H CF₃ Me OCHF₂ 2286. H H OCHF₂ Me CF₃ 2287. H H CF₃ Me OCH₂CHF₂ 2288. H H CF₃ Me OCH₂CF₃ 2289. H H CF₃ Me OCH₂CN 2290. H H CF₃ Me SO₂Me 2291. H H CF₃ Me SEt 2292. H H CF₃ Me Me 2293. H H CF₃ Me Et 2294. H H CF₃ Et Cl 2295. H H Cl Et CF₃ 2296. H H CF₃ iPr Cl 2297. H H Cl iPr CF₃ 2298. H H CF₃ tBu Cl 2299. H H Cl tBu CF₃ 2300. H H CF₃ cPen Cl 2301. H H Cl cPen CF₃ 2302. H H CF₃ CH₂cPr Cl 2303. H H Cl CH₂cPr CF₃ 2304. H H CF₃ CH₂CH═CH₂ Cl 2305. H H Cl CH₂CH═CH₂ CF₃ 2306. H H CF₃ CHF₂ OMe 2307. H H OMe CHF₂ CF₃ 2308. H H CF₃ CH₂CF₃ Cl 2309. H H Cl CH₂CF₃ CF₃ 2310. H H CF₃ CH₂OMe Cl 2311. H H Cl CH₂OMe CF₃ 2312. H H CF₃ CH₂CN Cl 2313. H H Me Ph Me 2314. H H Me Ph Cl 2315. H H Et Ph Cl 2316. H H Pr Ph Cl 2317. H H iPr Ph Cl 2318. H H CF₃ Ph Cl 2319. H H CF₃ Ph Me 2320. H H CF₃ Ph CF₃ 2321. H H CF₃ Ph F 2322. H H CF₃ Ph OMe 2323. H H CF₃ Ph OEt 2324. H H CF₃ Ph OCHF₂ 2325. H H CF₃ Ph CN 2326. H H CF₃ Ph(4-Cl) Cl 2327. H H Me Me OCH₂CF₃ 2328. H H CF₃ Me

2329. H H CF₃ Me H 2330. H H CF₃ Me OCH₂CH₂OMe 2331. H H CF₃ Me SMe 2332. H H CF₃ Me OCH₂CH₂CH₂F 2333. H H CF₃ Me OCH(CH₂F)₂ 2334. H H CF₃ Me OCH₂CF₂CHF₂ 2335. H H CF₃ Me OCH₂CF═CH₂ 2336. H H CF₃ Me OCH(Me)CF₃ 2337. H H CF₃ Me OCH(Me)CH₂F 2338. H H OCH₂CF₃ Me CF₃ 2339. H H OCH₂CF₃ Me CHF₂ 2340. H H CHF₂ Me CHF₂ 2341. H H CF₃ Me CHF₂ 2342. H H Cl Me OCHF₂ 2343. H H Br Me OCHF₂ 2344. H H Br Me CF₃ 2345. H H CF₃ Me CF₃ 2346. H H CHF₂ Me CF₃ 2347. H H CF₂CF₃ Me CF₃ 2348. H H CF₃ Me CF₂CF₃ 2349. H H CHF₂ Me OCH₂CF₃ 2350. H H CHF₂ Me OCHF₂ 2351. F H CF₃ Ph Cl 2352. F H CF₃ tBu Cl 2353. F H CF₃ CHF₂ Cl 2354. F H Cl CHF₂ CF₃ 2355. F H CF₃ Me OMe 2356. F H CF₃ Me CN 2357. F H Cl Et Cl 2358. F H CHF₂ Me Cl 2359. F H Me Me Me 2360. F H Me Me Cl 2361. F H Cl Me Cl 2362. F H CF₃ Me Cl 2363. F H Cl Me CF₃ 2364. F H CF₃ Me F 2365. F H OMe Me CF₃ 2366. F H CF₃ Me OEt 2367. F H CF₃ Me OCHF₂ 2368. F H OCHF₂ Me CF₃ 2369. F H CF₃ Me OCH₂CHF₂ 2370. F H CF₃ Me OCH₂CF₃ 2371. F H CF₃ Me OCH₂CN 2372. F H CF₃ Me SO₂Me 2373. F H CF₃ Me SEt 2374. F H CF₃ Me Me 2375. F H CF₃ Me Et 2376. F H CF₃ Et Cl 2377. F H Cl Et CF₃ 2378. F H CF₃ iPr Cl 2379. F H Cl iPr CF₃ 2380. F H CF₃ tBu Cl 2381. F H Cl tBu CF₃ 2382. F H CF₃ cPen Cl 2383. F H Cl cPen CF₃ 2384. F H CF₃ CH₂cPr Cl 2385. F H Cl CH₂cPr CF₃ 2386. F H CF₃ CH₂CH═CH₂ Cl 2387. F H Cl CH₂CH═CH₂ CF₃ 2388. F H CF₃ CHF₂ OMe 2389. F H OMe CHF₂ CF₃ 2390. F H CF₃ CH₂CF₃ Cl 2391. F H Cl CH₂CF₃ CF₃ 2392. F H CF₃ CH₂OMe Cl 2393. F H Cl CH₂OMe CF₃ 2394. F H CF₃ CH₂CN Cl 2395. F H Me Ph Me 2396. F H Me Ph Cl 2397. F H Et Ph Cl 2398. F H Pr Ph Cl 2399. F H iPr Ph Cl 2400. F H CF₃ Ph Cl 2401. F H CF₃ Ph Me 2402. F H CF₃ Ph CF₃ 2403. F H CF₃ Ph F 2404. F H CF₃ Ph OMe 2405. F H CF₃ Ph OEt 2406. F H CF₃ Ph OCHF₂ 2407. F H CF₃ Ph CN 2408. F H CF₃ Ph(4-Cl) Cl 2409. F H Me Me OCH₂CF₃ 2410. F H CF₃ Me

2411. F H CF₃ Me H 2412. F H CF₃ Me OCH₂CH₂OMe 2413. F H CF₃ Me SMe 2414. F H CF₃ Me OCH₂CH₂CH₂F 2415. F H CF₃ Me OCH(CH₂F)₂ 2416. F H CF₃ Me OCH₂CF₂CHF₂ 2417. F H CF₃ Me OCH₂CF═CH₂ 2418. F H CF₃ Me OCH(Me)CF₃ 2419. F H CF₃ Me OCH(Me)CH₂F 2420. F H OCH₂CF₃ Me CF₃ 2421. F H OCH₂CF₃ Me CHF₂ 2422. F H CHF₂ Me CHF₂ 2423. F H CF₃ Me CHF₂ 2424. F H Cl Me OCHF₂ 2425. F H Br Me OCHF₂ 2426. F H Br Me CF₃ 2427. F H CF₃ Me CF₃ 2428. F H CHF₂ Me CF₃ 2429. F H CF₂CF₃ Me CF₃ 2430. F H CF₃ Me CF₂CF₃ 2431. F H CHF₂ Me OCH₂CF₃ 2432. F H CHF₂ Me OCHF₂ 2433. Cl H CF₃ Ph Cl 2434. Cl H CF₃ tBu Cl 2435. Cl H CF₃ CHF₂ Cl 2436. Cl H Cl CHF₂ CF₃ 2437. Cl H CF₃ Me OMe 2438. Cl H CF₃ Me CN 2439. Cl H Cl Et Cl 2440. Cl H CHF₂ Me Cl 2441. Cl H Me Me Me 2442. Cl H Me Me Cl 2443. Cl H Cl Me Cl 2444. Cl H CF₃ Me Cl 2445. Cl H Cl Me CF₃ 2446. Cl H CF₃ Me F 2447. Cl H OMe Me CF₃ 2448. Cl H CF₃ Me OEt 2449. Cl H CF₃ Me OCHF₂ 2450. Cl H OCHF₂ Me CF₃ 2451. Cl H CF₃ Me OCH₂CHF₂ 2452. Cl H CF₃ Me OCH₂CF₃ 2453. Cl H CF₃ Me OCH₂CN 2454. Cl H CF₃ Me SO₂Me 2455. Cl H CF₃ Me SEt 2456. Cl H CF₃ Me Me 2457. Cl H CF₃ Me Et 2458. Cl H CF₃ Et Cl 2459. Cl H Cl Et CF₃ 2460. Cl H CF₃ iPr Cl 2461. Cl H Cl iPr CF₃ 2462. Cl H CF₃ tBu Cl 2463. Cl H Cl tBu CF₃ 2464. Cl H CF₃ cPen Cl 2465. Cl H Cl cPen CF₃ 2466. Cl H CF₃ CH₂cPr Cl 2467. Cl H Cl CH₂cPr CF₃ 2468. Cl H CF₃ CH₂CH═CH₂ Cl 2469. Cl H Cl CH₂CH═CH₂ CF₃ 2470. Cl H CF₃ CHF₂ OMe 2471. Cl H OMe CHF₂ CF₃ 2472. Cl H CF₃ CH₂CF₃ Cl 2473. Cl H Cl CH₂CF₃ CF₃ 2474. Cl H CF₃ CH₂OMe Cl 2475. Cl H Cl CH₂OMe CF₃ 2476. Cl H CF₃ CH₂CN Cl 2477. Cl H Me Ph Me 2478. Cl H Me Ph Cl 2479. Cl H Et Ph Cl 2480. Cl H Pr Ph Cl 2481. Cl H iPr Ph Cl 2482. Cl H CF₃ Ph Cl 2483. Cl H CF₃ Ph Me 2484. Cl H CF₃ Ph CF₃ 2485. Cl H CF₃ Ph F 2486. Cl H CF₃ Ph OMe 2487. Cl H CF₃ Ph OEt 2488. Cl H CF₃ Ph OCHF₂ 2489. Cl H CF₃ Ph CN 2490. Cl H CF₃ Ph(4-Cl) Cl 2491. Cl H Me Me OCH₂CF₃ 2492. Cl H CF₃ Me

2493. Cl H CF₃ Me H 2494. Cl H CF₃ Me OCH₂CH₂OMe 2495. Cl H CF₃ Me SMe 2496. Cl H CF₃ Me OCH₂CH₂CH₂F 2497. Cl H CF₃ Me OCH(CH₂F)₂ 2498. Cl H CF₃ Me OCH₂CF₂CHF₂ 2499. Cl H CF₃ Me OCH₂CF═CH₂ 2500. Cl H CF₃ Me OCH(Me)CF₃ 2501. Cl H CF₃ Me OCH(Me)CH₂F 2502. Cl H OCH₂CF₃ Me CF₃ 2503. Cl H OCH₂CF₃ Me CHF₂ 2504. Cl H CHF₂ Me CHF₂ 2505. Cl H CF₃ Me CHF₂ 2506. Cl H Cl Me OCHF₂ 2507. Cl H Br Me OCHF₂ 2508. Cl H Br Me CF₃ 2509. Cl H CF₃ Me CF₃ 2510. Cl H CHF₂ Me CF₃ 2511. Cl H CF₂CF₃ Me CF₃ 2512. Cl H CF₃ Me CF₂CF₃ 2513. Cl H CHF₂ Me OCH₂CF₃ 2514. Cl H CHF₂ Me OCHF₂ 2515. Br H CF₃ Ph Cl 2516. Br H CF₃ tBu Cl 2517. Br H CF₃ CHF₂ Cl 2518. Br H Cl CHF₂ CF₃ 2519. Br H CF₃ Me OMe 2520. Br H CF₃ Me CN 2521. Br H Cl Et Cl 2522. Br H CHF₂ Me Cl 2523. Br H Me Me Me 2524. Br H Me Me Cl 2525. Br H Cl Me Cl 2526. Br H CF₃ Me Cl 2527. Br H Cl Me CF₃ 2528. Br H CF₃ Me F 2529. Br H OMe Me CF₃ 2530. Br H CF₃ Me OEt 2531. Br H CF₃ Me OCHF₂ 2532. Br H OCHF₂ Me CF₃ 2533. Br H CF₃ Me OCH₂CHF₂ 2534. Br H CF₃ Me OCH₂CF₃ 2535. Br H CF₃ Me OCH₂CN 2536. Br H CF₃ Me SO₂Me 2537. Br H CF₃ Me SEt 2538. Br H CF₃ Me Me 2539. Br H CF₃ Me Et 2540. Br H CF₃ Et Cl 2541. Br H Cl Et CF₃ 2542. Br H CF₃ iPr Cl 2543. Br H Cl iPr CF₃ 2544. Br H CF₃ tBu Cl 2545. Br H Cl tBu CF₃ 2546. Br H CF₃ cPen Cl 2547. Br H Cl cPen CF₃ 2548. Br H CF₃ CH₂cPr Cl 2549. Br H Cl CH₂cPr CF₃ 2550. Br H CF₃ CH₂CH═CH₂ Cl 2551. Br H Cl CH₂CH═CH₂ CF₃ 2552. Br H CF₃ CHF₂ OMe 2553. Br H OMe CHF₂ CF₃ 2554. Br H CF₃ CH₂CF₃ Cl 2555. Br H Cl CH₂CF₃ CF₃ 2556. Br H CF₃ CH₂OMe Cl 2557. Br H Cl CH₂OMe CF₃ 2558. Br H CF₃ CH₂CN Cl 2559. Br H Me Ph Me 2560. Br H Me Ph Cl 2561. Br H Et Ph Cl 2562. Br H Pr Ph Cl 2563. Br H iPr Ph Cl 2564. Br H CF₃ Ph Cl 2565. Br H CF₃ Ph Me 2566. Br H CF₃ Ph CF₃ 2567. Br H CF₃ Ph F 2568. Br H CF₃ Ph OMe 2569. Br H CF₃ Ph OEt 2570. Br H CF₃ Ph OCHF₂ 2571. Br H CF₃ Ph CN 2572. Br H CF₃ Ph(4-Cl) Cl 2573. Br H Me Me OCH₂CF₃ 2574. Br H CF₃ Me

2575. Br H CF₃ Me H 2576. Br H CF₃ Me OCH₂CH₂OMe 2577. Br H CF₃ Me SMe 2578. Br H CF₃ Me OCH₂CH₂CH₂F 2579. Br H CF₃ Me OCH(CH₂F)₂ 2580. Br H CF₃ Me OCH₂CF₂CHF₂ 2581. Br H CF₃ Me OCH₂CF═CH₂ 2582. Br H CF₃ Me OCH(Me)CF₃ 2583. Br H CF₃ Me OCH(Me)CH₂F 2584. Br H OCH₂CF₃ Me CF₃ 2585. Br H OCH₂CF₃ Me CHF₂ 2586. Br H CHF₂ Me CHF₂ 2587. Br H CF₃ Me CHF₂ 2588. Br H Cl Me OCHF₂ 2589. Br H Br Me OCHF₂ 2590. Br H Br Me CF₃ 2591. Br H CF₃ Me CF₃ 2592. Br H CHF₂ Me CF₃ 2593. Br H CF₂CF₃ Me CF₃ 2594. Br H CF₃ Me CF₂CF₃ 2595. Br H CHF₂ Me OCH₂CF₃ 2596. Br H CHF₂ Me OCHF₂ 2597. I H CF₃ Ph Cl 2598. I H CF₃ tBu Cl 2599. I H CF₃ CHF₂ Cl 2600. I H Cl CHF₂ CF₃ 2601. I H CF₃ Me OMe 2602. I H CF₃ Me CN 2603. I H Cl Et Cl 2604. I H CHF₂ Me Cl 2605. I H Me Me Me 2606. I H Me Me Cl 2607. I H Cl Me Cl 2608. I H CF₃ Me Cl 2609. I H Cl Me CF₃ 2610. I H CF₃ Me F 2611. I H OMe Me CF₃ 2612. I H CF₃ Me OEt 2613. I H CF₃ Me OCHF₂ 2614. I H OCHF₂ Me CF₃ 2615. I H CF₃ Me OCH₂CHF₂ 2616. I H CF₃ Me OCH₂CF₃ 2617. I H CF₃ Me OCH₂CN 2618. I H CF₃ Me SO₂Me 2619. I H CF₃ Me SEt 2620. I H CF₃ Me Me 2621. I H CF₃ Me Et 2622. I H CF₃ Et Cl 2623. I H Cl Et CF₃ 2624. I H CF₃ iPr Cl 2625. I H Cl iPr CF₃ 2626. I H CF₃ tBu Cl 2627. I H Cl tBu CF₃ 2628. I H CF₃ cPen Cl 2629. I H Cl cPen CF₃ 2630. I H CF₃ CH₂cPr Cl 2631. I H Cl CH₂cPr CF₃ 2632. I H CF₃ CH₂CH═CH₂ Cl 2633. I H Cl CH₂CH═CH₂ CF₃ 2634. I H CF₃ CHF₂ OMe 2635. I H OMe CHF₂ CF₃ 2636. I H CF₃ CH₂CF₃ Cl 2637. I H Cl CH₂CF₃ CF₃ 2638. I H CF₃ CH₂OMe Cl 2639. I H Cl CH₂OMe CF₃ 2640. I H CF₃ CH₂CN Cl 2641. I H Me Ph Me 2642. I H Me Ph Cl 2643. I H Et Ph Cl 2644. I H Pr Ph Cl 2645. I H iPr Ph Cl 2646. I H CF₃ Ph Cl 2647. I H CF₃ Ph Me 2648. I H CF₃ Ph CF₃ 2649. I H CF₃ Ph F 2650. I H CF₃ Ph OMe 2651. I H CF₃ Ph OEt 2652. I H CF₃ Ph OCHF₂ 2653. I H CF₃ Ph CN 2654. I H CF₃ Ph(4-Cl) Cl 2655. I H Me Me OCH₂CF₃ 2656. I H CF₃ Me

2657. I H CF₃ Me H 2658. I H CF₃ Me OCH₂CH₂OMe 2659. I H CF₃ Me SMe 2660. I H CF₃ Me OCH₂CH₂CH₂F 2661. I H CF₃ Me OCH(CH₂F)₂ 2662. I H CF₃ Me OCH₂CF₂CHF₂ 2663. I H CF₃ Me OCH₂CF═CH₂ 2664. I H CF₃ Me OCH(Me)CF₃ 2665. I H CF₃ Me OCH(Me)CH₂F 2666. I H OCH₂CF₃ Me CF₃ 2667. I H OCH₂CF₃ Me CHF₂ 2668. I H CHF₂ Me CHF₂ 2669. I H CF₃ Me CHF₂ 2670. I H Cl Me OCHF₂ 2671. I H Br Me OCHF₂ 2672. I H Br Me CF₃ 2673. I H CF₃ Me CF₃ 2674. I H CHF₂ Me CF₃ 2675. I H CF₂CF₃ Me CF₃ 2676. I H CF₃ Me CF₂CF₃ 2677. I H CHF₂ Me OCH₂CF₃ 2678. I H CHF₂ Me OCHF₂ 2679. H F CF₃ Ph Cl 2680. H F CF₃ tBu Cl 2681. H F CF₃ CHF₂ Cl 2682. H F Cl CHF₂ CF₃ 2683. H F CF₃ Me OMe 2684. H F CF₃ Me CN 2685. H F Cl Et Cl 2686. H F CHF₂ Me Cl 2687. H F Me Me Me 2688. H F Me Me Cl 2689. H F Cl Me Cl 2690. H F CF₃ Me Cl 2691. H F Cl Me CF₃ 2692. H F CF₃ Me F 2693. H F OMe Me CF₃ 2694. H F CF₃ Me OEt 2695. H F CF₃ Me OCHF₂ 2696. H F OCHF₂ Me CF₃ 2697. H F CF₃ Me OCH₂CHF₂ 2698. H F CF₃ Me OCH₂CF₃ 2699. H F CF₃ Me OCH₂CN 2700. H F CF₃ Me SO₂Me 2701. H F CF₃ Me SEt 2702. H F CF₃ Me Me 2703. H F CF₃ Me Et 2704. H F CF₃ Et Cl 2705. H F Cl Et CF₃ 2706. H F CF₃ iPr Cl 2707. H F Cl iPr CF₃ 2708. H F CF₃ tBu Cl 2709. H F Cl tBu CF₃ 2710. H F CF₃ cPen Cl 2711. H F Cl cPen CF₃ 2712. H F CF₃ CH₂cPr Cl 2713. H F Cl CH₂cPr CF₃ 2714. H F CF₃ CH₂CH═CH₂ Cl 2715. H F Cl CH₂CH═CH₂ CF₃ 2716. H F CF₃ CHF₂ OMe 2717. H F OMe CHF₂ CF₃ 2718. H F CF₃ CH₂CF₃ Cl 2719. H F Cl CH₂CF₃ CF₃ 2720. H F CF₃ CH₂OMe Cl 2721. H F Cl CH₂OMe CF₃ 2722. H F CF₃ CH₂CN Cl 2723. H F Me Ph Me 2724. H F Me Ph Cl 2725. H F Et Ph Cl 2726. H F Pr Ph Cl 2727. H F iPr Ph Cl 2728. H F CF₃ Ph Cl 2729. H F CF₃ Ph Me 2730. H F CF₃ Ph CF₃ 2731. H F CF₃ Ph F 2732. H F CF₃ Ph OMe 2733. H F CF₃ Ph OEt 2734. H F CF₃ Ph OCHF₂ 2735. H F CF₃ Ph CN 2736. H F CF₃ Ph(4-Cl) Cl 2737. H F Me Me OCH₂CF₃ 2738. H F CF₃ Me

2739. H F CF₃ Me H 2740. H F CF₃ Me OCH₂CH₂OMe 2741. H F CF₃ Me SMe 2742. H F CF₃ Me OCH₂CH₂CH₂F 2743. H F CF₃ Me OCH(CH₂F)₂ 2744. H F CF₃ Me OCH₂CF₂CHF₂ 2745. H F CF₃ Me OCH₂CF═CH₂ 2746. H F CF₃ Me OCH(Me)CF₃ 2747. H F CF₃ Me OCH(Me)CH₂F 2748. H F OCH₂CF₃ Me CF₃ 2749. H F OCH₂CF₃ Me CHF₂ 2750. H F CHF₂ Me CHF₂ 2751. H F CF₃ Me CHF₂ 2752. H F Cl Me OCHF₂ 2753. H F Br Me OCHF₂ 2754. H F Br Me CF₃ 2755. H Cl CF₃ tBu Cl 2756. H Cl CF₃ CHF₂ Cl 2757. H Cl Cl CHF₂ CF₃ 2758. H Cl CF₃ Me OMe 2759. H Cl CF₃ Me CN 2760. H Cl CHF₂ Me Cl 2761. H Cl Me Me Me 2762. H Cl Me Me Cl 2763. H Cl CF₃ Me Cl 2764. H Cl Cl Me CF₃ 2765. H Cl CF₃ Me F 2766. H Cl OMe Me CF₃ 2767. H Cl CF₃ Me OCHF₂ 2768. H Cl OCHF₂ Me CF₃ 2769. H Cl CF₃ Me OCH₂CHF₂ 2770. H Cl CF₃ Me OCH₂CF₃ 2771. H Cl CF₃ Me SO₂Me 2772. H Cl CF₃ Me SEt 2773. H Cl CF₃ Et Cl 2774. H Cl CF₃ iPr Cl 2775. H Cl CF₃ tBu Cl 2776. H Cl Cl tBu CF₃ 2777. H Cl CF₃ cPen Cl 2778. H Cl CF₃ CHF₂ OMe 2779. H Cl CF₃ CH₂CF₃ Cl 2780. H Cl CF₃ Ph OCHF₂ 2781. H Cl CF₃ Ph Cl 2782. H Cl Me Me OCH₂CF₃ 2783. H Cl CF₃ Me

2784. H Cl CF₃ Me H 2785. H Cl CF₃ Me OCH₂CH₂OMe 2786. H Cl CF₃ Me SMe 2787. H Cl CF₃ Me OCH₂CH₂CH₂F 2788. H Cl CF₃ Me OCH(CH₂F)₂ 2789. H Cl CF₃ Me OCH₂CF₂CHF₂ 2790. H Cl CF₃ Me OCH₂CF═CH₂ 2791. H Cl CF₃ Me OCH(Me)CF₃ 2792. H Cl CF₃ Me OCH(Me)CH₂F 2793. H Cl OCH₂CF₃ Me CF₃ 2794. H Cl OCH₂CF₃ Me CHF₂ 2795. H Cl CHF₂ Me CHF₂ 2796. H Cl CF₃ Me CHF₂ 2797. H Cl Cl Me OCHF₂ 2798. H Cl Br Me OCHF₂ 2799. H Cl Br Me CF₃ 2800. H Br CF₃ tBu Cl 2801. H Br CF₃ CHF₂ Cl 2802. H Br Cl CHF₂ CF₃ 2803. H Br CF₃ Me OMe 2804. H Br CF₃ Me CN 2805. H Br CHF₂ Me Cl 2806. H Br Me Me Me 2807. H Br Me Me Cl 2808. H Br CF₃ Me Cl 2809. H Br Cl Me CF₃ 2810. H Br CF₃ Me F 2811. H Br OMe Me CF₃ 2812. H Br CF₃ Me OCHF₂ 2813. H Br OCHF₂ Me CF₃ 2814. H Br CF₃ Me OCH₂CHF₂ 2815. H Br CF₃ Me OCH₂CF₃ 2816. H Br CF₃ Me SO₂Me 2817. H Br CF₃ Me SEt 2818. H Br CF₃ Et Cl 2819. H Br CF₃ iPr Cl 2820. H Br CF₃ tBu Cl 2821. H Br Cl tBu CF₃ 2822. H Br CF₃ cPen Cl 2823. H Br CF₃ CHF₂ OMe 2824. H Br CF₃ CH₂CF₃ Cl 2825. H Br CF₃ Ph OCHF₂ 2826. H Br CF₃ Ph Cl 2827. H Br Me Me OCH₂CF₃ 2828. H Br CF₃ Me

2829. H Br CF₃ Me H 2830. H Br CF₃ Me OCH₂CH₂OMe 2831. H Br CF₃ Me SMe 2832. H Br CF₃ Me OCH₂CH₂CH₂F 2833. H Br CF₃ Me OCH(CH₂F)₂ 2834. H Br CF₃ Me OCH₂CF₂CHF₂ 2835. H Br CF₃ Me OCH₂CF═CH₂ 2836. H Br CF₃ Me OCH(Me)CF₃ 2837. H Br CF₃ Me OCH(Me)CH₂F 2838. H Br OCH₂CF₃ Me CF₃ 2839. H Br OCH₂CF₃ Me CHF₂ 2840. H Br CHF₂ Me CHF₂ 2841. H Br CF₃ Me CHF₂ 2842. H Br Cl Me OCHF₂ 2843. H Br Br Me OCHF₂ 2844. H Br Br Me CF₃ 2845. Me H CF₃ tBu Cl 2846. Me H CF₃ CHF₂ Cl 2847. Me H Cl CHF₂ CF₃ 2848. Me H CF₃ Me OMe 2849. Me H CF₃ Me CN 2850. Me H CHF₂ Me Cl 2851. Me H Me Me Me 2852. Me H Me Me Cl 2853. Me H CF₃ Me Cl 2854. Me H Cl Me CF₃ 2855. Me H CF₃ Me F 2856. Me H OMe Me CF₃ 2857. Me H CF₃ Me OCHF₂ 2858. Me H OCHF₂ Me CF₃ 2859. Me H CF₃ Me OCH₂CHF₂ 2860. Me H CF₃ Me OCH₂CF₃ 2861. Me H CF₃ Me SO₂Me 2862. Me H CF₃ Me SEt 2863. Me H CF₃ Et Cl 2864. Me H CF₃ iPr Cl 2865. Me H CF₃ tBu Cl 2866. Me H Cl tBu CF₃ 2867. Me H CF₃ cPen Cl 2868. Me H CF₃ CHF₂ OMe 2869. Me H CF₃ CH₂CF₃ Cl 2870. Me H CF₃ Ph OCHF₂ 2871. Me H CF₃ Ph Cl 2872. Me H Me Me OCH₂CF₃ 2873. Me H CF₃ Me

2874. Me H CF₃ Me H 2875. Me H CF₃ Me OCH₂CH₂OMe 2876. Me H CF₃ Me SMe 2877. Me H CF₃ Me OCH₂CH₂CH₂F 2878. Me H CF₃ Me OCH(CH₂F)₂ 2879. Me H CF₃ Me OCH₂CF₂CHF₂ 2880. Me H CF₃ Me OCH₂CF═CH₂ 2881. Me H CF₃ Me OCH(Me)CF₃ 2882. Me H CF₃ Me OCH(Me)CH₂F 2883. Me H OCH₂CF₃ Me CF₃ 2884. Me H OCH₂CF₃ Me CHF₂ 2885. Me H CHF₂ Me CHF₂ 2886. Me H CF₃ Me CHF₂ 2887. Me H Cl Me OCHF₂ 2888. Me H Br Me OCHF₂ 2889. Me H Br Me CF₃ 2890. NO₂ H CF₃ tBu Cl 2891. NO₂ H CF₃ CHF₂ Cl 2892. NO₂ H Cl CHF₂ CF₃ 2893. NO₂ H CF₃ Me OMe 2894. NO₂ H CF₃ Me CN 2895. NO₂ H CHF₂ Me Cl 2896. NO₂ H Me Me Me 2897. NO₂ H Me Me Cl 2898. NO₂ H CF₃ Me Cl 2899. NO₂ H Cl Me CF₃ 2900. NO₂ H CF₃ Me F 2901. NO₂ H OMe Me CF₃ 2902. NO₂ H CF₃ Me OCHF₂ 2903. NO₂ H OCHF₂ Me CF₃ 2904. NO₂ H CF₃ Me OCH₂CHF₂ 2905. NO₂ H CF₃ Me OCH₂CF₃ 2906. NO₂ H CF₃ Me SO₂Me 2907. NO₂ H CF₃ Me SEt 2908. NO₂ H CF₃ Et Cl 2909. NO₂ H CF₃ iPr Cl 2910. NO₂ H CF₃ tBu Cl 2911. NO₂ H Cl tBu CF₃ 2912. NO₂ H CF₃ cPen Cl 2913. NO₂ H CF₃ CHF₂ OMe 2914. NO₂ H CF₃ CH₂CF₃ Cl 2915. NO₂ H CF₃ Ph OCHF₂ 2916. NO₂ H CF₃ Ph Cl 2917. NO₂ H Me Me OCH₂CF₃ 2918. NO₂ H CF₃ Me

2919. NO₂ H CF₃ Me H 2920. NO₂ H CF₃ Me OCH₂CH₂OMe 2921. NO₂ H CF₃ Me SMe 2922. NO₂ H CF₃ Me OCH₂CH₂CH₂F 2923. NO₂ H CF₃ Me OCH(CH₂F)₂ 2924. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 2925. NO₂ H CF₃ Me OCH₂CF═CH₂ 2926. NO₂ H CF₃ Me OCH(Me)CF₃ 2927. NO₂ H CF₃ Me OCH(Me)CH₂F 2928. NO₂ H OCH₂CF₃ Me CF₃ 2929. NO₂ H OCH₂CF₃ Me CHF₂ 2930. NO₂ H CHF₂ Me CHF₂ 2931. NO₂ H CF₃ Me CHF₂ 2932. NO₂ H Cl Me OCHF₂ 2933. NO₂ H Br Me OCHF₂ 2934. NO₂ H Br Me CF₃ 2935. Cl Cl CF₃ tBu Cl 2936. Cl Cl CF₃ CHF₂ Cl 2937. Cl Cl Cl CHF₂ CF₃ 2938. Cl Cl CF₃ Me OMe 2939. Cl Cl CF₃ Me CN 2940. Cl Cl CHF₂ Me Cl 2941. Cl Cl Me Me Me 2942. Cl Cl Me Me Cl 2943. Cl Cl CF₃ Me Cl 2944. Cl Cl Cl Me CF₃ 2945. Cl Cl CF₃ Me F 2946. Cl Cl OMe Me CF₃ 2947. Cl Cl CF₃ Me OCHF₂ 2948. Cl Cl OCHF₂ Me CF₃ 2949. Cl Cl CF₃ Me OCH₂CHF₂ 2950. Cl Cl CF₃ Me OCH₂CF₃ 2951. Cl Cl CF₃ Me SO₂Me 2952. Cl Cl CF₃ Me SEt 2953. Cl Cl CF₃ Et Cl 2954. Cl Cl CF₃ iPr Cl 2955. Cl Cl CF₃ tBu Cl 2956. Cl Cl Cl tBu CF₃ 2957. Cl Cl CF₃ cPen Cl 2958. Cl Cl CF₃ CHF₂ OMe 2959. Cl Cl CF₃ CH₂CF₃ Cl 2960. Cl Cl CF₃ Ph OCHF₂ 2961. Cl Cl CF₃ Ph Cl 2962. Cl Cl Me Me OCH₂CF₃ 2963. Cl Cl CF₃ Me

2964. Cl Cl CF₃ Me H 2965. Cl Cl CF₃ Me OCH₂CH₂OMe 2966. Cl Cl CF₃ Me SMe 2967. Cl Cl CF₃ Me OCH₂CH₂CH₂F 2968. Cl Cl CF₃ Me OCH(CH₂F)₂ 2969. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 2970. Cl Cl CF₃ Me OCH₂CF═CH₂ 2971. Cl Cl CF₃ Me OCH(Me)CF₃ 2972. Cl Cl CF₃ Me OCH(Me)CH₂F 2973. Cl Cl OCH₂CF₃ Me CF₃ 2974. Cl Cl OCH₂CF₃ Me CHF₂ 2975. Cl Cl CHF₂ Me CHF₂ 2976. Cl Cl CF₃ Me CHF₂ 2977. Cl Cl Cl Me OCHF₂ 2978. Cl Cl Br Me OCHF₂ 2979. Cl Cl Br Me CF₃ 2980. Cl Me CF₃ tBu Cl 2981. Cl Me CF₃ CHF₂ Cl 2982. Cl Me Cl CHF₂ CF₃ 2983. Cl Me CF₃ Me OMe 2984. Cl Me CF₃ Me CN 2985. Cl Me CHF₂ Me Cl 2986. Cl Me Me Me Me 2987. Cl Me Me Me Cl 2988. Cl Me CF₃ Me Cl 2989. Cl Me Cl Me CF₃ 2990. Cl Me CF₃ Me F 2991. Cl Me OMe Me CF₃ 2992. Cl Me CF₃ Me OCHF₂ 2993. Cl Me OCHF₂ Me CF₃ 2994. Cl Me CF₃ Me OCH₂CHF₂ 2995. Cl Me CF₃ Me OCH₂CF₃ 2996. Cl Me CF₃ Me SO₂Me 2997. Cl Me CF₃ Me SEt 2998. Cl Me CF₃ Et Cl 2999. Cl Me CF₃ iPr Cl 3000. Cl Me CF₃ tBu Cl 3001. Cl Me Cl tBu CF₃ 3002. Cl Me CF₃ cPen Cl 3003. Cl Me CF₃ CHF₂ OMe 3004. Cl Me CF₃ CH₂CF₃ Cl 3005. Cl Me CF₃ Ph OCHF₂ 3006. Cl Me CF₃ Ph Cl 3007. Cl Me Me Me OCH₂CF₃ 3008. Cl Me CF₃ Me

3009. Cl Me CF₃ Me H 3010. Cl Me CF₃ Me OCH₂CH₂OMe 3011. Cl Me CF₃ Me SMe 3012. Cl Me CF₃ Me OCH₂CH₂CH₂F 3013. Cl Me CF₃ Me OCH(CH₂F)₂ 3014. Cl Me CF₃ Me OCH₂CF₂CHF₂ 3015. Cl Me CF₃ Me OCH₂CF═CH₂ 3016. Cl Me CF₃ Me OCH(Me)CF₃ 3017. Cl Me CF₃ Me OCH(Me)CH₂F 3018. Cl Me OCH₂CF₃ Me CF₃ 3019. Cl Me OCH₂CF₃ Me CHF₂ 3020. Cl Me CHF₂ Me CHF₂ 3021. Cl Me CF₃ Me CHF₂ 3022. Cl Me Cl Me OCHF₂ 3023. Cl Me Br Me OCHF₂ 3024. Cl Me Br Me CF₃

TABLE 3 Compounds of the formula (III-R) (III-R)

Ex. No. R¹ R² R³ R⁴ R⁵ 3025. H H CF₃ Ph Cl 3026. H H CF₃ tBu Cl 3027. H H CF₃ CHF₂ Cl 3028. H H Cl CHF₂ CF₃ 3029. H H CF₃ Me OMe 3030. H H CF₃ Me CN 3031. H H Cl Et Cl 3032. H H CHF₂ Me Cl 3033. H H Me Me Me 3034. H H Me Me Cl 3035. H H Cl Me Cl 3036. H H CF₃ Me Cl 3037. H H Cl Me CF₃ 3038. H H CF₃ Me F 3039. H H OMe Me CF₃ 3040. H H CF₃ Me OEt 3041. H H CF₃ Me OCHF₂ 3042. H H OCHF₂ Me CF₃ 3043. H H CF₃ Me OCH₂CHF₂ 3044. H H CF₃ Me OCH₂CF₃ 3045. H H CF₃ Me OCH₂CN 3046. H H CF₃ Me SO₂Me 3047. H H CF₃ Me SEt 3048. H H CF₃ Me Me 3049. H H CF₃ Me Et 3050. H H CF₃ Et Cl 3051. H H Cl Et CF₃ 3052. H H CF₃ iPr Cl 3053. H H Cl iPr CF₃ 3054. H H CF₃ tBu Cl 3055. H H Cl tBu CF₃ 3056. H H CF₃ cPen Cl 3057. H H Cl cPen CF₃ 3058. H H CF₃ CH₂cPr Cl 3059. H H Cl CH₂cPr CF₃ 3060. H H CF₃ CH₂CH═CH₂ Cl 3061. H H Cl CH₂CH═CH₂ CF₃ 3062. H H CF₃ CHF₂ OMe 3063. H H OMe CHF₂ CF₃ 3064. H H CF₃ CH₂CF₃ Cl 3065. H H Cl CH₂CF₃ CF₃ 3066. H H CF₃ CH₂OMe Cl 3067. H H Cl CH₂OMe CF₃ 3068. H H CF₃ CH₂CN Cl 3069. H H Me Ph Me 3070. H H Me Ph Cl 3071. H H Et Ph Cl 3072. H H Pr Ph Cl 3073. H H iPr Ph Cl 3074. H H CF₃ Ph Cl 3075. H H CF₃ Ph Me 3076. H H CF₃ Ph CF₃ 3077. H H CF₃ Ph F 3078. H H CF₃ Ph OMe 3079. H H CF₃ Ph OEt 3080. H H CF₃ Ph OCHF₂ 3081. H H CF₃ Ph CN 3082. H H CF₃ Ph(4-Cl) Cl 3083. H H Me Me OCH₂CF₃ 3084. H H CF₃ Me

3085. H H CF₃ Me H 3086. H H CF₃ Me OCH₂CH₂OMe 3087. H H CF₃ Me SMe 3088. H H CF₃ Me OCH₂CH₂CH₂F 3089. H H CF₃ Me OCH(CH₂F)₂ 3090. H H CF₃ Me OCH₂CF₂CHF₂ 3091. H H CF₃ Me OCH₂CF═CH₂ 3092. H H CF₃ Me OCH(Me)CF₃ 3093. H H CF₃ Me OCH(Me)CH₂F 3094. H H OCH₂CF₃ Me CF₃ 3095. H H OCH₂CF₃ Me CHF₂ 3096. H H CHF₂ Me CHF₂ 3097. H H CF₃ Me CHF₂ 3098. H H Cl Me OCHF₂ 3099. H H Br Me OCHF₂ 3100. H H Br Me CF₃ 3101. H H CF₃ Me CF₃ 3102. H H CHF₂ Me CF₃ 3103. H H CF₂CF₃ Me CF₃ 3104. H H CF₃ Me CF₂CF₃ 3105. H H CHF₂ Me OCH₂CF₃ 3106. H H CHF₂ Me OCHF₂ 3107. F H CF₃ Ph Cl 3108. F H CF₃ tBu Cl 3109. F H CF₃ CHF₂ Cl 3110. F H Cl CHF₂ CF₃ 3111. F H CF₃ Me OMe 3112. F H CF₃ Me CN 3113. F H Cl Et Cl 3114. F H CHF₂ Me Cl 3115. F H Me Me Me 3116. F H Me Me Cl 3117. F H Cl Me Cl 3118. F H CF₃ Me Cl 3119. F H Cl Me CF₃ 3120. F H CF₃ Me F 3121. F H OMe Me CF₃ 3122. F H CF₃ Me OEt 3123. F H CF₃ Me OCHF₂ 3124. F H OCHF₂ Me CF₃ 3125. F H CF₃ Me OCH₂CHF₂ 3126. F H CF₃ Me OCH₂CF₃ 3127. F H CF₃ Me OCH₂CN 3128. F H CF₃ Me SO₂Me 3129. F H CF₃ Me SEt 3130. F H CF₃ Me Me 3131. F H CF₃ Me Et 3132. F H CF₃ Et Cl 3133. F H Cl Et CF₃ 3134. F H CF₃ iPr Cl 3135. F H Cl iPr CF₃ 3136. F H CF₃ tBu Cl 3137. F H Cl tBu CF₃ 3138. F H CF₃ cPen Cl 3139. F H Cl cPen CF₃ 3140. F H CF₃ CH₂cPr Cl 3141. F H Cl CH₂cPr CF₃ 3142. F H CF₃ CH₂CH═CH₂ Cl 3143. F H Cl CH₂CH═CH₂ CF₃ 3144. F H CF₃ CHF₂ OMe 3145. F H OMe CHF₂ CF₃ 3146. F H CF₃ CH₂CF₃ Cl 3147. F H Cl CH₂CF₃ CF₃ 3148. F H CF₃ CH₂OMe Cl 3149. F H Cl CH₂OMe CF₃ 3150. F H CF₃ CH₂CN Cl 3151. F H Me Ph Me 3152. F H Me Ph Cl 3153. F H Et Ph Cl 3154. F H Pr Ph Cl 3155. F H iPr Ph Cl 3156. F H CF₃ Ph Cl 3157. F H CF₃ Ph Me 3158. F H CF₃ Ph CF₃ 3159. F H CF₃ Ph F 3160. F H CF₃ Ph OMe 3161. F H CF₃ Ph OEt 3162. F H CF₃ Ph OCHF₂ 3163. F H CF₃ Ph CN 3164. F H CF₃ Ph(4-Cl) Cl 3165. F H Me Me OCH₂CF₃ 3166. F H CF₃ Me

3167. F H CF₃ Me H 3168. F H CF₃ Me OCH₂CH₂OMe 3169. F H CF₃ Me SMe 3170. F H CF₃ Me OCH₂CH₂CH₂F 3171. F H CF₃ Me OCH(CH₂F)₂ 3172. F H CF₃ Me OCH₂CF₂CHF₂ 3173. F H CF₃ Me OCH₂CF═CH₂ 3174. F H CF₃ Me OCH(Me)CF₃ 3175. F H CF₃ Me OCH(Me)CH₂F 3176. F H OCH₂CF₃ Me CF₃ 3177. F H OCH₂CF₃ Me CHF₂ 3178. F H CHF₂ Me CHF₂ 3179. F H CF₃ Me CHF₂ 3180. F H Cl Me OCHF₂ 3181. F H Br Me OCHF₂ 3182. F H Br Me CF₃ 3183. F H CF₃ Me CF₃ 3184. F H CHF₂ Me CF₃ 3185. F H CF₂CF₃ Me CF₃ 3186. F H CF₃ Me CF₂CF₃ 3187. F H CHF₂ Me OCH₂CF₃ 3188. F H CHF₂ Me OCHF₂ 3189. Cl H CF₃ Ph Cl 3190. Cl H CF₃ tBu Cl 3191. Cl H CF₃ CHF₂ Cl 3192. Cl H Cl CHF₂ CF₃ 3193. Cl H CF₃ Me OMe 3194. Cl H CF₃ Me CN 3195. Cl H Cl Et Cl 3196. Cl H CHF₂ Me Cl 3197. Cl H Me Me Me 3198. Cl H Me Me Cl 3199. Cl H Cl Me Cl 3200. Cl H CF₃ Me Cl 3201. Cl H Cl Me CF₃ 3202. Cl H CF₃ Me F 3203. Cl H OMe Me CF₃ 3204. Cl H CF₃ Me OEt 3205. Cl H CF₃ Me OCHF₂ 3206. Cl H OCHF₂ Me CF₃ 3207. Cl H CF₃ Me OCH₂CHF₂ 3208. Cl H CF₃ Me OCH₂CF₃ 3209. Cl H CF₃ Me OCH₂CN 3210. Cl H CF₃ Me SO₂Me 3211. Cl H CF₃ Me SEt 3212. Cl H CF₃ Me Me 3213. Cl H CF₃ Me Et 3214. Cl H CF₃ Et Cl 3215. Cl H Cl Et CF₃ 3216. Cl H CF₃ iPr Cl 3217. Cl H Cl iPr CF₃ 3218. Cl H CF₃ tBu Cl 3219. Cl H Cl tBu CF₃ 3220. Cl H CF₃ cPen Cl 3221. Cl H Cl cPen CF₃ 3222. Cl H CF₃ CH₂cPr Cl 3223. Cl H Cl CH₂cPr CF₃ 3224. Cl H CF₃ CH₂CH═CH₂ Cl 3225. Cl H Cl CH₂CH═CH₂ CF₃ 3226. Cl H CF₃ CHF₂ OMe 3227. Cl H OMe CHF₂ CF₃ 3228. Cl H CF₃ CH₂CF₃ Cl 3229. Cl H Cl CH₂CF₃ CF₃ 3230. Cl H CF₃ CH₂OMe Cl 3231. Cl H Cl CH₂OMe CF₃ 3232. Cl H CF₃ CH₂CN Cl 3233. Cl H Me Ph Me 3234. Cl H Me Ph Cl 3235. Cl H Et Ph Cl 3236. Cl H Pr Ph Cl 3237. Cl H iPr Ph Cl 3238. Cl H CF₃ Ph Cl 3239. Cl H CF₃ Ph Me 3240. Cl H CF₃ Ph CF₃ 3241. Cl H CF₃ Ph F 3242. Cl H CF₃ Ph OMe 3243. Cl H CF₃ Ph OEt 3244. Cl H CF₃ Ph OCHF₂ 3245. Cl H CF₃ Ph CN 3246. Cl H CF₃ Ph(4-Cl) Cl 3247. Cl H Me Me OCH₂CF₃ 3248. Cl H CF₃ Me

3249. Cl H CF₃ Me H 3250. Cl H CF₃ Me OCH₂CH₂OMe 3251. Cl H CF₃ Me SMe 3252. Cl H CF₃ Me OCH₂CH₂CH₂F 3253. Cl H CF₃ Me OCH(CH₂F)₂ 3254. Cl H CF₃ Me OCH₂CF₂CHF₂ 3255. Cl H CF₃ Me OCH₂CF═CH₂ 3256. Cl H CF₃ Me OCH(Me)CF₃ 3257. Cl H CF₃ Me OCH(Me)CH₂F 3258. Cl H OCH₂CF₃ Me CF₃ 3259. Cl H OCH₂CF₃ Me CHF₂ 3260. Cl H CHF₂ Me CHF₂ 3261. Cl H CF₃ Me CHF₂ 3262. Cl H Cl Me OCHF₂ 3263. Cl H Br Me OCHF₂ 3264. Cl H Br Me CF₃ 3265. Cl H CF₃ Me CF₃ 3266. Cl H CHF₂ Me CF₃ 3267. Cl H CF₂CF₃ Me CF₃ 3268. Cl H CF₃ Me CF₂CF₃ 3269. Cl H CHF₂ Me OCH₂CF₃ 3270. Cl H CHF₂ Me OCHF₂ 3271. Br H CF₃ Ph Cl 3272. Br H CF₃ tBu Cl 3273. Br H CF₃ CHF₂ Cl 3274. Br H Cl CHF₂ CF₃ 3275. Br H CF₃ Me OMe 3276. Br H CF₃ Me CN 3277. Br H Cl Et Cl 3278. Br H CHF₂ Me Cl 3279. Br H Me Me Me 3280. Br H Me Me Cl 3281. Br H Cl Me Cl 3282. Br H CF₃ Me Cl 3283. Br H Cl Me CF₃ 3284. Br H CF₃ Me F 3285. Br H OMe Me CF₃ 3286. Br H CF₃ Me OEt 3287. Br H CF₃ Me OCHF₂ 3288. Br H OCHF₂ Me CF₃ 3289. Br H CF₃ Me OCH₂CHF₂ 3290. Br H CF₃ Me OCH₂CF₃ 3291. Br H CF₃ Me OCH₂CN 3292. Br H CF₃ Me SO₂Me 3293. Br H CF₃ Me SEt 3294. Br H CF₃ Me Me 3295. Br H CF₃ Me Et 3296. Br H CF₃ Et Cl 3297. Br H Cl Et CF₃ 3298. Br H CF₃ iPr Cl 3299. Br H Cl iPr CF₃ 3300. Br H CF₃ tBu Cl 3301. Br H Cl tBu CF₃ 3302. Br H CF₃ cPen Cl 3303. Br H Cl cPen CF₃ 3304. Br H CF₃ CH₂cPr Cl 3305. Br H Cl CH₂cPr CF₃ 3306. Br H CF₃ CH₂CH═CH₂ Cl 3307. Br H Cl CH₂CH═CH₂ CF₃ 3308. Br H CF₃ CHF₂ OMe 3309. Br H OMe CHF₂ CF₃ 3310. Br H CF₃ CH₂CF₃ Cl 3311. Br H Cl CH₂CF₃ CF₃ 3312. Br H CF₃ CH₂OMe Cl 3313. Br H Cl CH₂OMe CF₃ 3314. Br H CF₃ CH₂CN Cl 3315. Br H Me Ph Me 3316. Br H Me Ph Cl 3317. Br H Et Ph Cl 3318. Br H Pr Ph Cl 3319. Br H iPr Ph Cl 3320. Br H CF₃ Ph Cl 3321. Br H CF₃ Ph Me 3322. Br H CF₃ Ph CF₃ 3323. Br H CF₃ Ph F 3324. Br H CF₃ Ph OMe 3325. Br H CF₃ Ph OEt 3326. Br H CF3 Ph OCHF₂ 3327. Br H CF₃ Ph CN 3328. Br H CF₃ Ph(4-Cl) Cl 3329. Br H Me Me OCH₂CF₃ 3330. Br H CF₃ Me

3331. Br H CF₃ Me H 3332. Br H CF₃ Me OCH₂CH₂OMe 3333. Br H CF₃ Me SMe 3334. Br H CF₃ Me OCH₂CH₂CH₂F 3335. Br H CF₃ Me OCH(CH₂F)₂ 3336. Br H CF₃ Me OCH₂CF₂CHF₂ 3337. Br H CF₃ Me OCH₂CF═CH₂ 3338. Br H CF₃ Me OCH(Me)CF₃ 3339. Br H CF₃ Me OCH(Me)CH₂F 3340. Br H OCH₂CF₃ Me CF₃ 3341. Br H OCH₂CF₃ Me CHF₂ 3342. Br H CHF₂ Me CHF₂ 3343. Br H CF₃ Me CHF₂ 3344. Br H Cl Me OCHF₂ 3345. Br H Br Me OCHF₂ 3346. Br H Br Me CF₃ 3347. Br H CF₃ Me CF₃ 3348. Br H CHF₂ Me CF₃ 3349. Br H CF₂CF₃ Me CF₃ 3350. Br H CF₃ Me CF₂CF₃ 3351. Br H CHF₂ Me OCH₂CF₃ 3352. Br H CHF₂ Me OCHF₂ 3353. I H CF₃ Ph Cl 3354. I H CF₃ tBu Cl 3355. I H CF₃ CHF₂ Cl 3356. I H Cl CHF₂ CF₃ 3357. I H CF₃ Me OMe 3358. I H CF₃ Me CN 3359. I H Cl Et Cl 3360. I H CHF₂ Me Cl 3361. I H Me Me Me 3362. I H Me Me Cl 3363. I H Cl Me Cl 3364. I H CF₃ Me Cl 3365. I H Cl Me CF₃ 3366. I H CF₃ Me F 3367. I H OMe Me CF₃ 3368. I H CF₃ Me OEt 3369. I H CF₃ Me OCHF₂ 3370. I H OCHF₂ Me CF₃ 3371. I H CF₃ Me OCH₂CHF₂ 3372. I H CF₃ Me OCH₂CF₃ 3373. I H CF₃ Me OCH₂CN 3374. I H CF₃ Me SO₂Me 3375. I H CF₃ Me SEt 3376. I H CF₃ Me Me 3377. I H CF₃ Me Et 3378. I H CF₃ Et Cl 3379. I H Cl Et CF₃ 3380. I H CF₃ iPr Cl 3381. I H Cl iPr CF₃ 3382. I H CF₃ tBu Cl 3383. I H Cl tBu CF₃ 3384. I H CF₃ cPen Cl 3385. I H Cl cPen CF₃ 3386. I H CF₃ CH₂cPr Cl 3387. I H Cl CH₂cPr CF₃ 3388. I H CF₃ CH₂CH═CH₂ Cl 3389. I H Cl CH₂CH═CH₂ CF₃ 3390. I H CF₃ CHF₂ OMe 3391. I H OMe CHF₂ CF₃ 3392. I H CF₃ CH₂CF₃ Cl 3393. I H Cl CH₂CF₃ CF₃ 3394. I H CF₃ CH₂OMe Cl 3395. I H Cl CH₂OMe CF₃ 3396. I H CF₃ CH₂CN Cl 3397. I H Me Ph Me 3398. I H Me Ph Cl 3399. I H Et Ph Cl 3400. I H Pr Ph Cl 3401. I H iPr Ph Cl 3402. I H CF₃ Ph Cl 3403. I H CF₃ Ph Me 3404. I H CF₃ Ph CF₃ 3405. I H CF₃ Ph F 3406. I H CF₃ Ph OMe 3407. I H CF₃ Ph OEt 3408. I H CF₃ Ph OCHF₂ 3409. I H CF₃ Ph CN 3410. I H CF₃ Ph(4-Cl) Cl 3411. I H Me Me OCH₂CF₃ 3412. I H CF₃ Me

3413. I H CF₃ Me H 3414. I H CF₃ Me OCH₂CH₂OMe 3415. I H CF₃ Me SMe 3416. I H CF₃ Me OCH₂CH₂CH₂F 3417. I H CF₃ Me OCH(CH₂F)₂ 3418. I H CF₃ Me OCH₂CF₂CHF₂ 3419. I H CF₃ Me OCH₂CF═CH₂ 3420. I H CF₃ Me OCH(Me)CF₃ 3421. I H CF₃ Me OCH(Me)CH₂F 3422. I H OCH₂CF₃ Me CF₃ 3423. I H OCH₂CF₃ Me CHF₂ 3424. I H CHF₂ Me CHF₂ 3425. I H CF₃ Me CHF₂ 3426. I H Cl Me OCHF₂ 3427. I H Br Me OCHF₂ 3428. I H Br Me CF₃ 3429. I H CF₃ Me CF₃ 3430. I H CHF₂ Me CF₃ 3431. I H CF₂CF₃ Me CF₃ 3432. I H CF₃ Me CF₂CF₃ 3433. I H CHF₂ Me OCH₂CF₃ 3434. I H CHF₂ Me OCHF₂ 3435. H F CF₃ Ph Cl 3436. H F CF₃ tBu Cl 3437. H F CF₃ CHF₂ Cl 3438. H F Cl CHF₂ CF₃ 3439. H F CF₃ Me OMe 3440. H F CF₃ Me CN 3441. H F Cl Et Cl 3442. H F CHF₂ Me Cl 3443. H F Me Me Me 3444. H F Me Me Cl 3445. H F Cl Me Cl 3446. H F CF₃ Me Cl 3447. H F Cl Me CF₃ 3448. H F CF₃ Me F 3449. H F OMe Me CF₃ 3450. H F CF₃ Me OEt 3451. H F CF₃ Me OCHF₂ 3452. H F OCHF₂ Me CF₃ 3453. H F CF₃ Me OCH₂CHF₂ 3454. H F CF₃ Me OCH₂CF₃ 3455. H F CF₃ Me OCH₂CN 3456. H F CF₃ Me SO₂Me 3457. H F CF₃ Me SEt 3458. H F CF₃ Me Me 3459. H F CF₃ Me Et 3460. H F CF₃ Et Cl 3461. H F Cl Et CF₃ 3462. H F CF₃ iPr Cl 3463. H F Cl iPr CF₃ 3464. H F CF₃ tBu Cl 3465. H F Cl tBu CF₃ 3466. H F CF₃ cPen Cl 3467. H F Cl cPen CF₃ 3468. H F CF₃ CH₂cPr Cl 3469. H F Cl CH₂cPr CF₃ 3470. H F CF₃ CH₂CH═CH₂ Cl 3471. H F Cl CH₂CH═CH₂ CF₃ 3472. H F CF₃ CHF₂ OMe 3473. H F OMe CHF₂ CF₃ 3474. H F CF₃ CH₂CF₃ Cl 3475. H F Cl CH₂CF₃ CF₃ 3476. H F CF₃ CH₂OMe Cl 3477. H F Cl CH₂OMe CF₃ 3478. H F CF₃ CH₂CN Cl 3479. H F Me Ph Me 3480. H F Me Ph Cl 3481. H F Et Ph Cl 3482. H F Pr Ph Cl 3483. H F iPr Ph Cl 3484. H F CF₃ Ph Cl 3485. H F CF₃ Ph Me 3486. H F CF₃ Ph CF₃ 3487. H F CF₃ Ph F 3488. H F CF₃ Ph OMe 3489. H F CF₃ Ph OEt 3490. H F CF₃ Ph OCHF₂ 3491. H F CF₃ Ph CN 3492. H F CF₃ Ph(4-Cl) Cl 3493. H F Me Me OCH₂CF₃ 3494. H F CF₃ Me

3495. H F CF₃ Me H 3496. H F CF₃ Me OCH₂CH₂OMe 3497. H F CF₃ Me SMe 3498. H F CF₃ Me OCH₂CH₂CH₂F 3499. H F CF₃ Me OCH(CH₂F)₂ 3500. H F CF₃ Me OCH₂CF₂CHF₂ 3501. H F CF₃ Me OCH₂CF═CH₂ 3502. H F CF₃ Me OCH(Me)CF₃ 3503. H F CF₃ Me OCH(Me)CH₂F 3504. H F OCH₂CF₃ Me CF₃ 3505. H F OCH₂CF₃ Me CHF₂ 3506. H F CHF₂ Me CHF₂ 3507. H F CF₃ Me CHF₂ 3508. H F Cl Me OCHF₂ 3509. H F Br Me OCHF₂ 3510. H F Br Me CF₃ 3511. H Cl CF₃ tBu Cl 3512. H Cl CF₃ CHF₂ Cl 3513. H Cl Cl CHF₂ CF₃ 3514. H Cl CF₃ Me OMe 3515. H Cl CF₃ Me CN 3516. H Cl CHF₂ Me Cl 3517. H Cl Me Me Me 3518. H Cl Me Me Cl 3519. H Cl CF₃ Me Cl 3520. H Cl Cl Me CF₃ 3521. H Cl CF₃ Me F 3522. H Cl OMe Me CF₃ 3523. H Cl CF₃ Me OCHF₂ 3524. H Cl OCHF₂ Me CF₃ 3525. H Cl CF₃ Me OCH₂CHF₂ 3526. H Cl CF₃ Me OCH₂CF₃ 3527. H Cl CF₃ Me SO₂Me 3528. H Cl CF₃ Me SEt 3529. H Cl CF₃ Et Cl 3530. H Cl CF₃ iPr Cl 3531. H Cl CF₃ tBu Cl 3532. H Cl Cl tBu CF₃ 3533. H Cl CF₃ cPen Cl 3534. H Cl CF₃ CHF₂ OMe 3535. H Cl CF₃ CH₂CF₃ Cl 3536. H Cl CF₃ Ph OCHF₂ 3537. H Cl CF₃ Ph Cl 3538. H Cl Me Me OCH₂CF₃ 3539. H Cl CF₃ Me

3540. H Cl CF₃ Me H 3541. H Cl CF₃ Me OCH₂CH₂OMe 3542. H Cl CF₃ Me SMe 3543. H Cl CF₃ Me OCH₂CH₂CH₂F 3544. H Cl CF₃ Me OCH(CH₂F)₂ 3545. H Cl CF₃ Me OCH₂CF₂CHF₂ 3546. H Cl CF₃ Me OCH₂CF═CH₂ 3547. H Cl CF₃ Me OCH(Me)CF₃ 3548. H Cl CF₃ Me OCH(Me)CH₂F 3549. H Cl OCH₂CF₃ Me CF₃ 3550. H Cl OCH₂CF₃ Me CHF₂ 3551. H Cl CHF₂ Me CHF₂ 3552. H Cl CF₃ Me CHF₂ 3553. H Cl Cl Me OCHF₂ 3554. H Cl Br Me OCHF₂ 3555. H Cl Br Me CF₃ 3556. H Br CF₃ tBu Cl 3557. H Br CF₃ CHF₂ Cl 3558. H Br Cl CHF₂ CF₃ 3559. H Br CF₃ Me OMe 3560. H Br CF₃ Me CN 3561. H Br CHF₂ Me Cl 3562. H Br Me Me Me 3563. H Br Me Me Cl 3564. H Br CF₃ Me Cl 3565. H Br Cl Me CF₃ 3566. H Br CF₃ Me F 3567. H Br OMe Me CF₃ 3568. H Br CF₃ Me OCHF₂ 3569. H Br OCHF₂ Me CF₃ 3570. H Br CF₃ Me OCH₂CHF₂ 3571. H Br CF₃ Me OCH₂CF₃ 3572. H Br CF₃ Me SO₂Me 3573. H Br CF₃ Me SEt 3574. H Br CF₃ Et Cl 3575. H Br CF₃ iPr Cl 3576. H Br CF₃ tBu Cl 3577. H Br Cl tBu CF₃ 3578. H Br CF₃ cPen Cl 3579. H Br CF₃ CHF₂ OMe 3580. H Br CF₃ CH₂CF₃ Cl 3581. H Br CF₃ Ph OCHF₂ 3582. H Br CF₃ Ph Cl 3583. H Br Me Me OCH₂CF₃ 3584. H Br CF₃ Me

3585. H Br CF₃ Me H 3586. H Br CF₃ Me OCH₂CH₂OMe 3587. H Br CF₃ Me SMe 3588. H Br CF₃ Me OCH₂CH₂CH₂F 3589. H Br CF₃ Me OCH(CH₂F)₂ 3590. H Br CF₃ Me OCH₂CF₂CHF₂ 3591. H Br CF₃ Me OCH₂CF═CH₂ 3592. H Br CF₃ Me OCH(Me)CF₃ 3593. H Br CF₃ Me OCH(Me)CH₂F 3594. H Br OCH₂CF₃ Me CF₃ 3595. H Br OCH₂CF₃ Me CHF₂ 3596. H Br CHF₂ Me CHF₂ 3597. H Br CF₃ Me CHF₂ 3598. H Br Cl Me OCHF₂ 3599. H Br Br Me OCHF₂ 3600. H Br Br Me CF₃ 3601. Me H CF₃ tBu Cl 3602. Me H CF₃ CHF₂ Cl 3603. Me H Cl CHF₂ CF₃ 3604. Me H CF₃ Me OMe 3605. Me H CF₃ Me CN 3606. Me H CHF₂ Me Cl 3607. Me H Me Me Me 3608. Me H Me Me Cl 3609. Me H CF₃ Me Cl 3610. Me H Cl Me CF₃ 3611. Me H CF₃ Me F 3612. Me H OMe Me CF₃ 3613. Me H CF₃ Me OCHF₂ 3614. Me H OCHF₂ Me CF₃ 3615. Me H CF₃ Me OCH₂CHF₂ 3616. Me H CF₃ Me OCH₂CF₃ 3617. Me H CF₃ Me SO₂Me 3618. Me H CF₃ Me SEt 3619. Me H CF₃ Et Cl 3620. Me H CF₃ iPr Cl 3621. Me H CF₃ tBu Cl 3622. Me H Cl tBu CF₃ 3623. Me H CF₃ cPen Cl 3624. Me H CF₃ CHF₂ OMe 3625. Me H CF₃ CH₂CF₃ Cl 3626. Me H CF₃ Ph OCHF₂ 3627. Me H CF₃ Ph Cl 3628. Me H Me Me OCH₂CF₃ 3629. Me H CF₃ Me

3630. Me H CF₃ Me H 3631. Me H CF₃ Me OCH₂CH₂OMe 3632. Me H CF₃ Me SMe 3633. Me H CF₃ Me OCH₂CH₂CH₂F 3634. Me H CF₃ Me OCH(CH₂F)₂ 3635. Me H CF₃ Me OCH₂CF₂CHF₂ 3636. Me H CF₃ Me OCH₂CF═CH₂ 3637. Me H CF₃ Me OCH(Me)CF₃ 3638. Me H CF₃ Me OCH(Me)CH₂F 3639. Me H OCH₂CF₃ Me CF₃ 3640. Me H OCH₂CF₃ Me CHF₂ 3641. Me H CHF₂ Me CHF₂ 3642. Me H CF₃ Me CHF₂ 3643. Me H Cl Me OCHF₂ 3644. Me H Br Me OCHF₂ 3645. Me H Br Me CF₃ 3646. NO₂ H CF₃ tBu Cl 3647. NO₂ H CF₃ CHF₂ Cl 3648. NO₂ H Cl CHF₂ CF₃ 3649. NO₂ H CF₃ Me OMe 3650. NO₂ H CF₃ Me CN 3651. NO₂ H CHF₂ Me Cl 3652. NO₂ H Me Me Me 3653. NO₂ H Me Me Cl 3654. NO₂ H CF₃ Me Cl 3655. NO₂ H Cl Me CF₃ 3656. NO₂ H CF₃ Me F 3657. NO₂ H OMe Me CF₃ 3658. NO₂ H CF₃ Me OCHF₂ 3659. NO₂ H OCHF₂ Me CF₃ 3660. NO₂ H CF₃ Me OCH₂CHF₂ 3661. NO₂ H CF₃ Me OCH₂CF₃ 3662. NO₂ H CF₃ Me SO₂Me 3663. NO₂ H CF₃ Me SEt 3664. NO₂ H CF₃ Et Cl 3665. NO₂ H CF₃ iPr Cl 3666. NO₂ H CF₃ tBu Cl 3667. NO₂ H Cl tBu CF₃ 3668. NO₂ H CF₃ cPen Cl 3669. NO₂ H CF₃ CHF₂ OMe 3670. NO₂ H CF₃ CH₂CF₃ Cl 3671. NO₂ H CF₃ Ph OCHF₂ 3672. NO₂ H CF₃ Ph Cl 3673. NO₂ H Me Me OCH₂CF₃ 3674. NO₂ H CF₃ Me

3675. NO₂ H CF₃ Me H 3676. NO₂ H CF₃ Me OCH₂CH₂OMe 3677. NO₂ H CF₃ Me SMe 3678. NO₂ H CF₃ Me OCH₂CH₂CH₂F 3679. NO₂ H CF₃ Me OCH(CH₂F)₂ 3680. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 3681. NO₂ H CF₃ Me OCH₂CF═CH₂ 3682. NO₂ H CF₃ Me OCH(Me)CF₃ 3683. NO₂ H CF₃ Me OCH(Me)CH₂F 3684. NO₂ H OCH₂CF₃ Me CF₃ 3685. NO₂ H OCH₂CF₃ Me CHF₂ 3686. NO₂ H CHF₂ Me CHF₂ 3687. NO₂ H CF₃ Me CHF₂ 3688. NO₂ H Cl Me OCHF₂ 3689. NO₂ H Br Me OCHF₂ 3690. NO₂ H Br Me CF₃ 3691. Cl Cl CF₃ tBu Cl 3692. Cl Cl CF₃ CHF₂ Cl 3693. Cl Cl Cl CHF₂ CF₃ 3694. Cl Cl CF₃ Me OMe 3695. Cl Cl CF₃ Me CN 3696. Cl Cl CHF₂ Me Cl 3697. Cl Cl Me Me Me 3698. Cl Cl Me Me Cl 3699. Cl Cl CF₃ Me Cl 3700. Cl Cl Cl Me CF₃ 3701. Cl Cl CF₃ Me F 3702. Cl Cl OMe Me CF₃ 3703. Cl Cl CF₃ Me OCHF₂ 3704. Cl Cl OCHF₂ Me CF₃ 3705. Cl Cl CF₃ Me OCH₂CHF₂ 3706. Cl Cl CF₃ Me OCH₂CF₃ 3707. Cl Cl CF₃ Me SO₂Me 3708. Cl Cl CF₃ Me SEt 3709. Cl Cl CF₃ Et Cl 3710. Cl Cl CF₃ iPr Cl 3711. Cl Cl CF₃ tBu Cl 3712. Cl Cl Cl tBu CF₃ 3713. Cl Cl CF₃ cPen Cl 3714. Cl Cl CF₃ CHF₂ OMe 3715. Cl Cl CF₃ CH₂CF₃ Cl 3716. Cl Cl CF₃ Ph OCHF₂ 3717. Cl Cl CF₃ Ph Cl 3718. Cl Cl Me Me OCH₂CF₃ 3719. Cl Cl CF₃ Me

3720. Cl Cl CF₃ Me H 3721. Cl Cl CF₃ Me OCH₂CH₂OMe 3722. Cl Cl CF₃ Me SMe 3723. Cl Cl CF₃ Me OCH₂CH₂CH₂F 3724. Cl Cl CF₃ Me OCH(CH₂F)₂ 3725. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 3726. Cl Cl CF₃ Me OCH₂CF═CH₂ 3727. Cl Cl CF₃ Me OCH(Me)CF₃ 3728. Cl Cl CF₃ Me OCH(Me)CH₂F 3729. Cl Cl OCH₂CF₃ Me CF₃ 3730. Cl Cl OCH₂CF₃ Me CHF₂ 3731. Cl Cl CHF₂ Me CHF₂ 3732. Cl Cl CF₃ Me CHF₂ 3733. Cl Cl Cl Me OCHF₂ 3734. Cl Cl Br Me OCHF₂ 3735. Cl Cl Br Me CF₃ 3736. Cl Me CF₃ tBu Cl 3737. Cl Me CF₃ CHF₂ Cl 3738. Cl Me Cl CHF₂ CF₃ 3739. Cl Me CF₃ Me OMe 3740. Cl Me CF₃ Me CN 3741. Cl Me CHF₂ Me Cl 3742. Cl Me Me Me Me 3743. Cl Me Me Me Cl 3744. Cl Me CF₃ Me Cl 3745. Cl Me Cl Me CF₃ 3746. Cl Me CF₃ Me F 3747. Cl Me OMe Me CF₃ 3748. Cl Me CF₃ Me OCHF₂ 3749. Cl Me OCHF₂ Me CF₃ 3750. Cl Me CF₃ Me OCH₂CHF₂ 3751. Cl Me CF₃ Me OCH₂CF₃ 3752. Cl Me CF₃ Me SO₂Me 3753. Cl Me CF₃ Me SEt 3754. Cl Me CF₃ Et Cl 3755. Cl Me CF₃ iPr Cl 3756. Cl Me CF₃ tBu Cl 3757. Cl Me Cl tBu CF₃ 3758. Cl Me CF₃ cPen Cl 3759. Cl Me CF₃ CHF₂ OMe 3760. Cl Me CF₃ CH₂CF₃ Cl 3761. Cl Me CF₃ Ph OCHF₂ 3762. Cl Me CF₃ Ph Cl 3763. Cl Me Me Me OCH₂CF₃ 3764. Cl Me CF₃ Me

3765. Cl Me CF₃ Me H 3766. Cl Me CF₃ Me OCH₂CH₂OMe 3767. Cl Me CF₃ Me SMe 3768. Cl Me CF₃ Me OCH₂CH₂CH₂F 3769. Cl Me CF₃ Me OCH(CH₂F)₂ 3770. Cl Me CF₃ Me OCH₂CF₂CHF₂ 3771. Cl Me CF₃ Me OCH₂CF═CH₂ 3772. Cl Me CF₃ Me OCH(Me)CF₃ 3773. Cl Me CF₃ Me OCH(Me)CH₂F 3774. Cl Me OCH₂CF₃ Me CF₃ 3775. Cl Me OCH₂CF₃ Me CHF₂ 3776. Cl Me CHF₂ Me CHF₂ 3777. Cl Me CF₃ Me CHF₂ 3778. Cl Me Cl Me OCHF₂ 3779. Cl Me Br Me OCHF₂ 3780. Cl Me Br Me CF₃

The NMR data were measured at 400 MHz and in CDCl₃ as solvent. The chemical shift δ is stated in ppm (reference TMS).

Retention times (R_(t), in minutes) and enantiomer ratios (ee) of chiral compounds were determined by analytical chiral HPLC [Chiralpak® IC column (250×4.6 mm, particle size 10 μm), temperature 25° C., flow rate 1 ml/min, n-heptane/2-propanol 80:20 v/v].

Data for Table 2:

Compound No. 2449: R_(t)=6.254 min.

Compound No. 2531: R_(t)=6.585 min.

Compound No. 2341: R_(t)=29.201 min [Chiralpak® IC column (250×4.6 mm, particle size 10 μm), temperature 25° C., flow rate 0.6 ml/min, n-heptane/2-propanol 90:10 v/v].

Compound No. 2288: R_(t)=6.912 min.

Data for Table 3:

Compound No. 3205: R_(t)=7.873 min.

Compound No. 3287: R_(t)=8.217 min.

Compound No. 3097: R_(t)=32.132 min [Chiralpak® IC column (250×4.6 mm, particle size 10 μm), temperature 25° C., flow rate 0.6 ml/min, n-heptane/2-propanol 90:10 v/v].

Compound No. 3044: R_(t)=13.384 min.

B. Formulation Examples

-   a) A dust is obtained by mixing 10 parts by weight of a compound of     the formula (I) and/or a salt thereof and 90 parts by weight of talc     as inert substance and comminuting the mixture in a hammer mill. -   b) A wettable powder which is readily dispersible in water is     obtained by mixing 25 parts by weight of a compound of the     formula (I) and/or a salt thereof, 64 parts by weight of     kaolin-containing quartz as inert substance, 10 parts by weight of     potassium lignosulfonate and 1 part by weight of sodium     oleoylmethyltaurinate as wetting agent and dispersant, and grinding     the mixture in a pinned-disk mill. -   c) A readily water-dispersible dispersion concentrate is obtained by     mixing 20 parts by weight of a compound of the formula (I) and/or a     salt thereof with 6 parts by weight of alkylphenol polyglycol ether     (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether     (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling     range for example about 255 to above 277° C.) and grinding the     mixture in a ball mill to a fineness of below 5 microns. -   d) An emulsifiable concentrate is obtained from 15 parts by weight     of a compound of the formula (I) and/or a salt thereof, 75 parts by     weight of cyclohexanone as solvent and 10 parts by weight of     oxethylated nonylphenol as emulsifier. -   e) Water-dispersible granules are obtained by mixing     -   75 parts by weight of a compound of the formula (I) and/or a         salt thereof,     -   10 parts by weight of calcium lignosulfonate,     -   5 parts by weight of sodium lauryl sulfate,     -   3 parts by weight of polyvinyl alcohol and     -   7 parts by weight of kaolin,     -   grinding the mixture in a pinned-disk mill, and granulating the         powder in a fluidized bed by spraying on water as granulating         liquid. -   f) Water-dispersible granules are also obtained by homogenizing and     precomminuting, in a colloid mill,     -   25 parts by weight of a compound of the formula (I) and/or a         salt thereof,     -   5 parts by weight of sodium         2,2′-dinaphthylmethane-6,6′-disulfonate,     -   2 parts by weight of sodium oleoylmethyltaurinate,     -   1 part by weight of polyvinyl alcohol,     -   17 parts by weight of calcium carbonate and     -   50 parts by weight of water,     -   subsequently grinding the mixture in a bead mill and atomizing         and drying the resulting suspension in a spray tower by means of         a single-substance nozzle.

C. Biological Examples

The compounds of the formula (I) according to the invention (and/or their salts), hereinbelow also referred to together as “compounds according to the invention”, have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants. The active compounds act efficiently even on perennial harmful plants which produce shoots from rhizomes, root stocks and other perennial organs and which are difficult to control.

The present invention therefore also relates to a method for controlling unwanted plants or for regulating the growth of plants, preferably in crops of plants, where one or more compound(s) according to the invention is/are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), to the seeds (for example grains, seeds or vegetative propagules such as tubers or shoot parts with buds) or to the area on which the plants grow (for example the area under cultivation). In this context, the compounds according to the invention can be applied for example pre-sowing (if appropriate also by incorporation into the soil), pre-emergence or post-emergence. Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention, without the enumeration being restricted to certain species.

Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

If the compounds according to the invention are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.

If the active compounds are applied post-emergence to the green parts of the plants, growth stops after the treatment, and the harmful plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

Although the compounds according to the invention display an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, in particular Zea and Triticum, are damaged only to an insignificant extent, or not at all, depending on the structure of the respective compound according to the invention and its application rate. This is why the present compounds are highly suitable for the selective control of unwanted plant growth in plant crops such as agriculturally useful plants or ornamentals.

Moreover, the compounds according to the invention (depending on their respective structure and the application rate applied) have outstanding growth-regulatory properties in crop plants. They engage in the plant's metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since for example lodging can be reduced, or prevented completely, hereby.

By virtue of their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis. In general, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.

With regard to transgenic crops, it is preferred to use the compounds according to the invention in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetable varieties.

It is preferred to employ the compounds according to the invention as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.

1. Pre-Emergence Herbicidal Effect and Crop Plant Compatibility

Seeds of monocotyledonous or dicotyledonous weed plants or crop plants are placed in sandy loam in wood-fiber pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP), are then applied as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent to the surface of the covering soil.

After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. After about 3 weeks, the effect of the preparations is scored visually in comparison with untreated controls (herbicidal effect in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of weed grasses and broad-leaved weeds. The compounds Nos. 35, 50, 51, 230, 542, 788, 789, 1034, 2285, 2449, 2531 and other compounds from Tables 1-3, for example, have very good herbicidal activity against harmful plants such as, for example, Avena fatua, Stellaria media, Echinochloa crus galli, Lolium multiflorum, Setaria viridis, Amaranthus retroflexus, Veronica persica, Matricaria inodora, Fallopia convolvulus and Alopecurus myosuroides when applied by the pre-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, compounds according to the invention applied by the pre-emergence method also spare dicotyledonous crops such as oilseed rape even at high active compound application rates. Some substances also spare gramineous crops such as corn. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the pre-emergence method.

2. Post-Emergence Herbicidal Effect and Crop Plant Compatibility

Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood-fiber pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds according to the invention, formulated in the form of wettable powders (WP), are then sprayed as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent onto the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations is rated visually in comparison to untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal post-emergence activity against a plurality of weed grasses and broad-leaved weeds. The compounds Nos. 35, 50, 51, 542, 230, 2285 and other compounds from Tables 1-3, for example, have very good herbicidal activity against harmful plants such as, for example, Echinochloa crus galli, Lolium multiflorum, and Setaria viridis when applied by the post-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, compounds according to the invention applied by the pre-emergence method also spare dicotyledonous crops such as oilseed rape even at high active compound application rates. Some substances also spare gramineous crops such as corn. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the post-emergence method. 

1. A compound of the formula (I) or an agrochemically acceptable salt thereof

in which the radicals and indices have the following meaning: n is 0, 1, 2; the substituents R¹ and R² are each independently of one another selected from the group consisting of hydrogen, halogen, nitro, cyano, formyl, —C(O)OH, hydroxyl, and amino; (C₁-C₆)-alkyl, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl and (C₁-C₆)-alkylcarbonyloxy; (C₁-C₆)-alkoxy, (C₁-C₆)-alkoxy-carbonyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy and (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy; (C₂-C₆)-alkenyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyl and (C₂-C₆)-alkynyloxy; (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl and (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy; mono-((C₁-C₆)-alkyl)amino, di-((C₁-C₆)-alkyl)amino, N—((C₁-C₆)-alkanoyl)amino, aminocarbonyl-(C₁-C₆)-alkyl, mono-((C₁-C₆)-alkyl)aminocarbonyl, di-((C₁-C₆)-alkyl)aminocarbonyl, mono-((C₁-C₆)-alkyl)aminosulfonyl and di-((C₁-C₆)-alkyl)aminosulfonyl; (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkylcarbonyl and (C₃-C₈)-cycloalkoxycarbonyl; (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy, (C₃-C₈)-cycloalkylthio, (C₃-C₈)-cycloalkylsulfinyl, (C₃-C₈)-cycloalkylsulfonyl and (C₃-C₈)-cycloalkyl sulfonyloxy; cyano-(C₁-C₆)-alkoxy and cyano-(C₁-C₆)-alkyl; —CONH—SO₂—(C₁-C₆)-alkyl, —NHCHO, —NHCO—(C₁-C₆)-alkyl, —NHCO₂—(C₁-C₆)-alkyl, —NHCONH—(C₁-C₆)-alkyl, —NHSO₂—(C₁-C₆)-alkyl, —OCONH—(C₁-C₆)-alkyl, (C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl, —C(O)NHR⁹, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are each independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an oxygen or a sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups, the substituents R³ to R⁵ are each independently of one another selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH and formyl; (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy, (C₁-C₆)-haloalkylcarbonyloxy, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl and (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl; (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-haloalkoxycarbonyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl and (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl; (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkenylcarbonyl, (C₂-C₆)-haloalkenylcarbonyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-alkenyloxycarbonyl and (C₂-C₆)-haloalkenyloxycarbonyl; (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₂-C₆)-alkynylcarbonyl, (C₂-C₆)-haloalkynylcarbonyl, (C₂-C₆)-alkynyloxy, (C₂-C₆)-haloalkynyloxy, (C₂-C₆)-alkynyloxycarbonyl and (C₂-C₆)-haloalkynyloxycarbonyl; (C₁-C₆)-alkylthiocarbonyl, (C₁-C₆)-haloalkylthiocarbonyl, (C₁-C₆)-alkylthiocarbonyloxy and (C₁-C₆)-halo-al-kyl-thio-carbonyloxy; (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy, (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyl and (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy; (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl, (C₆-C₁₄)-aryloxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy, (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyloxy, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy, (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-haloalkylsulfonyl, (C₁-C₆)-haloalkylthio, (C₁-C₆)-halo-alkylsulfinyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkyl-thio-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkylsulfonyloxy, (C₆-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio, (C₆-C₁₄)-arylsulfinyl, mono-((C₁-C₆)-alkyl)amino, mono-((C₁-C₆)-haloalkyl)amino, di-((C₁-C₆)-alkyl)amino, di-((C₁-C₆)-haloalkyl)amino, ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)amino, N—((C₁-C₆)-alkanoyl)amino, N—((C₁-C₆)-haloalkanoyl)amino, aminocarbonyl-(C₁-C₆)-alkyl, mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl, di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl and mono-((C₁-C₆)-alkyl)aminocarbonyl; (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkylcarbonyloxy, (C₃-C₈)-cycloalkoxycarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy and (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyloxy; (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkenylcarbonyl, (C₃-C₈)-cyclo-al-kenyloxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkenylcarbonyloxy, (C₃-C₈)-cycloalkenyloxycarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy and (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy; (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio, (C₃-C₈)-cyclo-alkenylthio and (C₃-C₆)-alkynylthio; hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkoxy and cyano-(C₁-C₆)-alkyl; 3-oxetanyloxy-, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are each independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an oxygen or a sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups, where the radicals R³ to R⁵ mentioned above may be mono- or polysubstituted independently of one another, and/or mutually adjacent radicals R⁴ and R⁵ may be cyclically attached to one another and/or form a (C₁-C₆)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C₁-C₆)-alkylene group may be mono- or polysubstituted by halogen and the respective halogen substituents may be identical or different.
 2. A compound as claimed in claim 1, wherein R¹ is selected from the group consisting of H, halogen, nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl, (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)aminocarbonyl, di-((C₁-C₄)-alkyl)aminocarbonyl, mono-((C₁-C₄)-alkyl)aminosulfonyl, di-((C₁-C₄)-alkyl)aminosulfonyl, (C₁-C₄)-alkylthio, (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cycloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy, (C₃-C₆)-cycloalkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl, —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, —CONR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl and (C₁-C₆)-haloalkyl, where the radical R¹ mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C₁-C₆)-alkyl.
 3. A compound as claimed in claim 1, wherein R² is selected i from the group consisting of H, halogen, nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl, (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)aminocarbonyl, di-((C₁-C₄)-alkyl)aminocarbonyl, mono-((C₁-C₄)-alkyl)aminosulfonyl, di-((C₁-C₄)-alkyl)aminosulfonyl, (C₁-C₄)-alkyl-thio, (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cyclo-alkyl-sul-fo-nyl, (C₁-C₄)-alkylsulfonyloxy, (C₃-C₆)-cycloalkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl, —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, —CONR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl and (C₁-C₆)-haloalkyl, where the radical R¹ mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C₁-C₆)-alkyl.
 4. A compound as claimed in claim 1, wherein R³ is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, hydroxyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl, phenyl, phenyl-(C₁-C₂)-alkyl, phenyl-(C₁-C₂)-alkoxy, phenoxy, (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C¹-C⁶)-alkylene group which may contain an oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups.
 5. A compound as claimed in claim 1, wherein R⁴ is selected from the group consisting of hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, phenyl, phenyl-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, where the cycloalkyl radical is optionally substituted by (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, cyano-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl, mono-(C₁-C₄)-alkylaminocarbonyl-C₁-C₂)-alkyl, di-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkylsulfonyl; phenylsulfonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyl; phenylcarbonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; and (C₁-C₄)-alkoxycarbonyl.
 6. A compound as claimed in claim 1, wherein R⁵ is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, cyano-(C₁-C₄)-alkyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxt, hydroxyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl; phenyl which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkyl which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; phenoxy which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyloxy-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl and 3-oxetanyloxy-, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups.
 7. A compound as claimed in claim 1, wherein n is
 1. 8. A compound as claimed in claim 7, wherein the compound of the formula (I) where n=1 is present in the (R) or (S) configuration in a stereochemical purity of more than 50% to 100%.
 9. A process for preparing a compound of the formula (III) or a compound of the formula (IV), wherein R¹, R², R³, R⁴, R⁵ have the meanings given in claim 1

by oxidation of a thioether of the formula (II) by means of an oxidizing agent,

wherein R¹, R², R³, R⁴, R⁵ have the meanings given in claim 1, wherein one equivalent of the oxidizing agent gives the sulfoxides of the formula (III) and two equivalents of an oxidizing agent gives the sulfones of formula (IV).
 10. A process for preparing a thioether of the formula (II)

in which R¹, R², R³, R⁴, R⁵ have the meanings given in claim 1, according to one of the processes below: (a) reaction of 2-mercaptooxazole or an oxazole-2(3H)-thione or a salt thereof

in which R¹, R² have the meanings given in claim 1, with a (1H-pyrazol-4-ylmethyl) derivative of the formula (VI)

in which R³, R⁴, R⁵ have the meanings given claim 1 and Lg is a leaving group, in the presence of an alkali metal or alkaline earth metal base or an organic base in a solvent; (b) reaction of an oxazole derivative of the formula (VII),

in which R¹, R² have the meanings given in claim 1 and Lg′ is a leaving group with a [(1H-pyrazol-4-ylmethyl)]imidothiocarbamate salt of the formula (VIII)

in which R³, R⁴, R⁵ have the meaning given in claim 1, Lg is a leaving group, in a one-pot process in the presence of an aqueous alkali metal or alkaline earth metal base or an alkali metal or alkaline earth metal carbonate base and a solvent; (c) reaction of an oxazole derivative of the formula (VII),

in which R¹, R² have the meanings given in claim 1 and Lg′ is a leaving group with a (1H-pyrazol-4-ylmethyl) mercaptan of the formula (IX)

in which R³, R⁴, R⁵ have the meanings given in claim 1 in the presence of an alkali metal or alkaline earth metal base; (d) reaction of an oxazole derivative of the formula (X),

in which R², R³, R⁴, R⁵ have the meanings given in claim 1 and R¹ is a halogen or NO₂ according to the formula scheme below:

(e) reaction of a (1H-pyrazol-4-ylmethyl) disulfide derivative of the formula (XV) with 2-amino-oxazoles of the formula (XIV) and a diazotizing agent as shown in the scheme below,

and in which R¹, R², R³, R⁴, R⁵ have the meanings given in claim
 1. 11. The process as claimed in claim 9 wherein the compound of the formula (II) obtained by the process as claimed in claim 10 is used as starting material in the process as claimed in claim
 9. 12. A composition comprising at least one compound of the formula (I) according to claim
 1. 13. The composition as claimed in claim 12 wherein the composition comprises at least one further active compound selected from the group consisting of at least one further herbicide and at least one safener.
 14. A method of regulating plant growth which comprises administering an effective amount of the compound of formula (I) according to claim
 1. 15. The method of claim 14 wherein the regulation of plant growth occurs within a specific crop plant.
 16. The compound of claim 2, wherein wherein R² is selected from the group consisting of H, halogen, nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl, (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)aminocarbonyl, di-((C₁-C₄)-alkyl)aminocarbonyl, mono-((C₁-C₄)-alkyl)aminosulfonyl, di-((C₁-C₄)-alkyl)aminosulfonyl, (C₁-C₄)-alkyl-thio, (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cyclo-alkyl-sul-fo-nyl, (C₁-C₄)-alkylsulfonyloxy, (C₃-C₆)-cycloalkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl, —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, —CONR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl and (C₁-C₆)-haloalkyl, where the radical R¹ mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C₁-C₆)-alkyl; R³ is selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, hydroxyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl, phenyl, phenyl-(C₁-C₂)-alkyl, phenyl-(C₁-C₂)-alkoxy, phenoxy, (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C¹-C⁶)-alkylene group which may contain an oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups; R⁴ is selected from the group consisting of hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, phenyl, phenyl-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, where the cycloalkyl radical is optionally substituted by (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, cyano-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl, mono-(C₁-C₄)-alkylaminocarbonyl-C₁-C₂)-alkyl, di-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkylsulfonyl; phenylsulfonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyl; phenylcarbonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; and (C₁-C₄)-alkoxycarbonyl; R⁵ is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, cyano-(C₁-C₄)-alkyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxt, hydroxyl-(C₁-C₂)-alkyl, hydroxyl-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl; phenyl which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; phenyl-(C₁-C₂)-alkyl which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; phenoxy which is optionally substituted by one or more identical of different radicals from the group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyloxy-(C₁-C₂)-alkyl, (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl and 3-oxetanyloxy-, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ are independently of one another are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain an oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups. 